Hot melt adhesive compositions containing polyolefin-polydiorganosiloxane copolymers and methods for preparing and using same

Abstract

To solve the problem in which: to increase productivity in assembly processes, such as electronic device assembly processes, there is an industrial need for hot melt adhesive compositions that have relatively low melt viscosity upon dispensing and quickly build green strength upon cooling.SOLUTION: A hot melt adhesive composition includes a polyolefin-polydiorganosiloxane block copolymer, a polydiorganosiloxane, and a polyorganosilicate resin. The hot melt adhesive composition is useful in electronic device assembly processes.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 62 / 644,826 and U.S. Provisional Patent Application No. 62 / 644,852, both filed March 19, 2018. Both U.S. Provisional Patent Application No. 62 / 644,826 and U.S. Provisional Patent Application No. 62 / 644,852 are incorporated herein by reference.

[0002] The polyolefin-polydiorganosiloxane block copolymers can be included in polyorganosiloxane hot melt adhesive compositions that can be hardened by cooling, curing, or both to form adhesives and / or sealants. The hot melt adhesive compositions are useful in electronic device assembly processes. [Background technology]

[0003] Conventional polyorganosiloxane hot melt adhesive compositions have the drawback of having insufficient green strength and creep resistance for certain applications. To improve green strength, hydrocarbon waxes have been added. However, polyorganosiloxane hot melt adhesive compositions containing such hydrocarbon waxes may have the drawback of insufficient green strength, and the addition of such hydrocarbon waxes does not sufficiently improve creep resistance.

[0004] To increase productivity in assembly processes, such as electronic device assembly processes, there is a need in the industry for hot melt adhesive compositions that have a relatively low melt viscosity when dispensed and that rapidly build green strength upon cooling. Summary of the Invention

[0005] The hot melt adhesive composition includes (A) a polyolefin-polydiorganosiloxane block copolymer (copolymer), (B) a polydiorganosiloxane, and (C) a polyorganosilicate resin. Also provided herein are methods for preparing the hot melt adhesive composition and methods for using the hot melt adhesive composition in an assembly process. DETAILED DESCRIPTION OF THE INVENTION

[0006] The hot melt adhesive composition comprises (A) a polyolefin-polydiorganosiloxane block copolymer, (B) a polydiorganosiloxane, and (C) a polyorganosilicate resin. The hot melt adhesive composition may be hardened by cooling, for example, without curing. Alternatively, the hot melt adhesive composition may be reactive, for example, by a hydrosilylation reaction, a condensation reaction, or a combination thereof. Reactive hot melt adhesive compositions harden by cooling and curing. The hot melt adhesive composition may further comprise one or more additional starting materials selected from the group consisting of (D) catalysts, (E) crosslinkers, (F) inhibitors, (G) vehicles, (H) moisture scavengers, (I) fillers, (J) colorants, (K) optical brighteners, (L) corrosion inhibitors, (M) heat stabilizers, and combinations of two or more of (E), (F), (G), (H), (I), (J), (K), (L), and (M), i.e., additional starting materials selected from the group consisting of When the hot melt adhesive composition is reactive, it typically comprises (D) catalysts and (E) crosslinkers in addition to (A) polyolefin-polydiorganosiloxane block copolymer, (B) polydiorganosiloxane, and (C) polyorganosilicate resin. When the hot melt adhesive composition is reactive, at least one of the (A) polyolefin-polydiorganosiloxane block copolymer, (B) polydiorganosiloxane, and (C) polyorganosilicate resin has a reactive substituent. When an (E) crosslinker is present, at least one of the (A) polyolefin-polydiorganosiloxane block copolymer, (B) polydiorganosiloxane, and (C) polyorganosilicate resin has a reactive substituent that can react with the reactive substituent on the (E) crosslinker. When an (E) crosslinker is not present in the reactive hot melt adhesive composition, at least two of the (A) polyolefin-polydiorganosiloxane block copolymer, (B) polydiorganosiloxane, and (C) polyorganosilicate resin have a reactive substituent.Alternatively, all of the starting materials (A), (B), and (C) may have reactive substituents in the reactive hot melt adhesive composition.

[0007] (A) Polyolefin-polydiorganosiloxane block copolymer The starting material (A) is a polyolefin-polydiorganosiloxane block copolymer. The polyolefin-polydiorganosiloxane block copolymer can be prepared as described in co-pending U.S. patent application Ser. No. 62 / 644,826, filed March 19, 2018, which is incorporated herein by reference. The polyolefin-polydiorganosiloxane block copolymer comprises: 1) A) A polyolefin having 1 to 2 terminal silyl groups per molecule, wherein the terminal silyl groups are represented by the formula [ka] wherein each R 1 is an independently selected monovalent hydrocarbyl group, and the subscript a is 1 or 2 (a silyl-terminated polyolefin); B) capable of reacting with silicon-bonded hydrogen atoms (R 2 a substantially linear polydiorganosiloxane having 1 to 2 hydrolyzable substituents (as described herein); C) a Lewis acid catalyst; and

[0008] The starting materials may optionally further comprise one or more additional starting materials selected from the group consisting of D) a solvent, E) an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom, and both D) and E).

[0009] Step 1) may be carried out by any convenient means, such as mixing at ambient pressure at a temperature of 50° C. to 200° C., alternatively 100° C. to 120° C. Step 1) may be carried out by any convenient means, such as solution processing (i.e., dissolving and / or dispersing the other starting materials in D) a solvent and heating), or melt extrusion (e.g., where no solvent is used or where the solvent is removed during processing).

[0010] This method may optionally further include one or more additional steps. For example, the method may further include 2) recovering the polyolefin-polydiorganosiloxane block copolymer after step 1). Recovery can be achieved by any convenient means, such as stripping and / or distillation, of unwanted materials, such as catalyst, by-products, and / or unreacted starting materials. Alternatively, recovery can be achieved by precipitation of the polyolefin-polydiorganosiloxane block copolymer in a non-solvent, whereby unwanted materials can be removed, optionally by washing with water.

[0011] A) Silyl-terminated polyolefin The starting material A) is a polyolefin having one to two terminal silyl groups per molecule (silyl-terminated polyolefin). The terminal silyl groups are represented by the formula (A1): [ka] wherein each R 1 is an independently selected monovalent hydrocarbyl group, and each subscript a is independently 1 or 2. 1 Suitable monovalent hydrocarbyl groups of may have 1 to 20 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. 1The hydrocarbyl group may be selected from the group consisting of an alkyl group, an alkenyl group, and an aryl group, or alternatively may be selected from the group consisting of alkyl and aryl; alternatively it may be alkyl. The alkyl group is exemplified by branched saturated monovalent hydrocarbyl groups having 6 or more carbon atoms such as methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, and cycloalkyl groups such as cyclopentyl and cyclohexyl. The alkenyl group is exemplified by, but not limited to, vinyl, allyl, butenyl (including n-butenyl, isobutenyl, and t-butenyl), and hexenyl (including their straight-chain and branched isomers). The aryl group is exemplified by cyclopentadienyl, phenyl, tolyl, xylyl, anthracenyl, benzyl, 1-phenylethyl, 2-phenylethyl, and naphthyl. The monocyclic aryl group may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms. The polycyclic aryl group may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms. Alternatively, each R 1 may be independently selected from the group consisting of alkyl and aryl, alternatively methyl and phenyl. Alternatively, each R 1 may be methyl.

[0012] Alternatively, the silyl-terminated polyolefin has the unit formula (A2): [Chemical formula] where the subscript a and R 1 are as defined above, the subscript f is 0 to 1, the subscripts t and u have relative values such that 0 < t ≦ 1 and 0 ≦ u ≦ 1, the subscript g is 1 or more, and each R etrepresents an ethylene unit, and each R O represents an olefin unit other than ethylene. O may be an alpha-olefin or a cyclic olefin. Examples of alpha-olefins are described below and include ethylene, propylene, and octene. Examples of cyclic olefins are described below and include ethylidene norbornene, norbornene, vinyl norbornene, cyclohexene, and cyclopentene. Alternatively, subscript g may be from 1 to 500, alternatively from 10 to 400, or alternatively from 18 to 360. Alternatively, subscript g may have a value sufficient to impart an Mn of 500 to 50,000 g / mol, alternatively from 500 to 10,000 g / mol to the silyl-terminated polyolefin.

[0013] Alternatively, the silyl-terminated polyolefin may have the unit formula (A3): [ka] wherein the subscripts a, f, g, t, and u, and R 1 is as above. Each R 7 are independently monovalent hydrocarbyl groups of 2 to 20 carbon atoms. 7 The monovalent hydrocarbyl group in R may be alkyl, alkenyl, or aryl, alternatively alkyl. 7 may be an alkyl group of 2 to 12 carbon atoms, and alternatively 2 to 6 carbon atoms. Alternatively, each R 7 is a hexyl group.

[0014] The starting material A), a silyl-terminated polyolefin, may have one terminal silyl group per molecule (i.e., subscript f=1). Examples of silyl-terminated polyolefins having a silyl group at one end of the polymer chain include dimethyl, hydrogen silyl-terminated polyethylene; dimethyl, hydrogen silyl-terminated poly(ethylene / octene) copolymer; methyl, dihydrogen silyl-terminated polyethylene; methyl, dihydrogen silyl-terminated poly(ethylene / octene) copolymer; diphenyl hydrogen silyl-terminated polyethylene; diphenyl hydrogen silyl-terminated poly(ethylene / octene) copolymer; phenyl dihydrogen silyl-terminated polyethylene; phenyl dihydrogen silyl-terminated poly(ethylene / octene) copolymer; chlorophenyl hydrogen silyl-terminated polyethylene; or chlorophenyl hydrogen silyl-terminated poly(ethylene / octene) copolymer. The silyl-terminated polyolefins can be prepared by the process described in co-pending U.S. patent application Ser. No. 62 / 644,635, filed Mar. 19, 2018, and U.S. patent application Ser. No. 62 / 644,624, filed Mar. 19, 2018, both of which are incorporated herein by reference.

[0015] Silyl-terminated polyolefins having one terminal silyl group per molecule can be prepared by a process comprising: 1) combining starting materials including a) a polymeryl metal, optionally b) a nitrogen-containing heterocycle, and c) a halosilane, thereby forming a product comprising a silyl-terminated polyolefin. The starting materials may optionally further comprise d) a solvent. The process may optionally further comprise one or more additional steps selected from 2) washing the product with water, and 3) recovering the product. a) The polymeryl metal is prepared by combining i) an olefin monomer, ii) a catalyst, and iii) a compound of formula R F N M, where M is a metal atom from Group 1, 2, 12, or 13 of the Periodic Table of Elements, and each R Fare independently monovalent hydrocarbyl groups of 1 to 20 carbon atoms, where the subscript N is 1 to the maximum valence of the metal selected for M. In certain embodiments, M may be a divalent metal, including but not limited to calcium (Ca), magnesium, and zinc (Zn), where in this embodiment the subscript N=2. In certain embodiments, M may be a trivalent metal, including but not limited to aluminum (Al), boron (B), and gallium (Ga), where in this embodiment the subscript N=3. Alternatively, M may be either Zn or Al, or alternatively, Zn. The monovalent hydrocarbyl groups of 1 to 20 carbon atoms may be alkyl groups (as defined herein), alternatively exemplified by ethyl, propyl, octyl, and combinations thereof. Suitable olefin monomers are disclosed, for example, in US Pat. No. 7,858,706, column 16, lines 5-36, and US Pat. No. 8,053,529, column 12, lines 7-41, which are incorporated herein by reference. Examples of suitable olefin monomers include linear or branched alpha-olefins of 2 to 30 carbon atoms, alternatively 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; cycloolefins of 3 to 30, alternatively 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. Alternatively, starting material i) may comprise ethylene and, optionally, one or more olefin monomers other than ethylene, such as propylene or 1-octene. Alternatively, the olefin monomers may be ethylene and 1-octene. Alternatively, the olefin monomer may be ethylene.Suitable catalysts (and optional cocatalysts) are disclosed, for example, in U.S. Pat. No. 7,858,706, column 19, line 45 to column 51, line 29, and in U.S. Pat. No. 8,053,529, column 16, line 37 to column 48, line 17, which are incorporated herein by reference. Suitable chain shuttling agents include trialkylaluminum and dialkylzinc compounds, such as triethylaluminum, tri(isopropyl)aluminum, tri(isobutyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, and diethylzinc. Suitable chain shuttling agents are disclosed in U.S. Pat. No. 7,858,706, column 16, line 37 to column 19, line 44, and in U.S. Pat. No. 8,053,529, column 12, line 49 to column 14, line 40, which are incorporated herein by reference.

[0016] Polymeryl metals useful for preparing silyl-terminated polyolefins can be prepared using known process conditions and equipment, such as those disclosed in U.S. Pat. No. 7,858,706 to Arriola et al., column 52, line 2 to column 57, line 21, and U.S. Pat. No. 8,053,529 to Carnahan et al.

[0017] For example, when the polymeryl metal is polymeryl-zinc and the halosilane is a chlorosilane, an optional nitrogen-containing heterocycle can be added. The optional nitrogen-containing heterocycle can be: [ka] and mixtures of two or more of b1), b2) and b3), wherein in formula b1), b2), and b3), R 2 is a monovalent hydrocarbyl group, and R 3 is a hydrogen atom or a monovalent hydrocarbyl group, and R 4 is a hydrogen atom or a monovalent hydrocarbyl group, and R 5 is a hydrogen atom or a monovalent hydrocarbyl group, and R 6is a hydrogen atom or a monovalent hydrocarbyl group, and R 7 is a hydrogen atom or a monovalent hydrocarbyl group, and R 8 is a hydrogen atom or a monovalent hydrocarbyl group, and R 9 is a hydrogen atom or a monovalent hydrocarbyl group, and D 2 is an amino-functional hydrocarbyl group or a group of the formula -NR 11 2 groups, where each R 11 is a monovalent hydrocarbyl group, and R 13 is a hydrogen atom or a monovalent hydrocarbyl group, and R 14 is a hydrogen atom or a monovalent hydrocarbyl group, and R 15 is a hydrogen atom or a monovalent hydrocarbyl group, and R 16 is a hydrogen atom or a monovalent hydrocarbyl group, and R 17 is a hydrogen atom or a monovalent hydrocarbyl group. 2 ~R 17 Suitable hydrocarbyl groups in R may have 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 4 carbon atoms, and alternatively 1 to 2 carbon atoms. 2 ~R 17 The hydrocarbyl group in may be an alkyl group. Alkyl groups are exemplified by methyl, ethyl, propyl (including branched and straight chain isomers thereof), butyl (including branched and straight chain isomers thereof), and hexyl; alternatively, by methyl. Alternatively, each R 3 ~R 10 may be selected from the group consisting of hydrogen and methyl. Alternatively, each R 13 ~R 17 may be hydrogen. The nitrogen-containing heterocycle used as the basic additive in the process may be [ka] pyridine N-oxide and mixtures of two or more of b4), b5) and b6).

[0018] If a nitrogen-containing heterocycle is used, the resulting product can be recovered, for example, by removing the nitrogen-containing heterocycle by washing with water before using the silyl-terminated polyolefin in the method for preparing the polyolefin-polydiorganosiloxane block copolymers described herein.

[0019] Halosilanes have the formula H J R 12 K Six (4-J-K) wherein each R 12 is independently selected from hydrogen and monovalent hydrocarbyl groups of 1 to 18 carbon atoms, each X is independently a halogen atom, the subscript J is 1 to 3, and the subscript K is 0 to 2, provided that the quantity (J+K) is ≦ 3. Examples of suitable halosilanes include, but are not limited to, dihalosilanes such as methylhydrogendichlorosilane, methylhydrogendiiodosilane, methylhydrogenchloroiodosilane, ethylhydrogendichlorosilane, ethylhydrogendibromosilane, ethylhydrogendiiodosilane, ethylhydrogenchloroiodosilane, propylhydrogendichlorosilane, propylhydrogendibromosilane, propylhydrogendiiodosilane, propylhydrogenchloroiodosilane, phenylhydrogendichlorosilane, phenylhydrogendiiodosilane, phenylhydrogendibromosilane, and mixtures thereof. Examples of suitable halosilanes include, but are not limited to, monohalosilanes such as dimethylhydrogenchlorosilane, dimethylhydrogenbromosilane, dimethylhydrogeniodosilane, diethylhydrogenchlorosilane, diethylhydrogeniodosilane, dipropylhydrogenchlorosilane, dipropylhydrogenbromosilane, dipropylhydrogeniodosilane, diphenylhydrogenchlorosilane, diphenylhydrogeniodosilane, diphenylhydrogenbromosilane, and mixtures thereof. Alternatively, the halosilane can be selected from the group consisting of c1) dimethylhydrogenchlorosilane, c2) diphenylhydrogenchlorosilane, c3) phenyldihydrogenchlorosilane, c4) phenylhydrogendichlorosilane, c5) dimethylhydrogeniodosilane, and mixtures of two or more of c1), c2), c3), c4), and c5).

[0020] Starting material (d) A solvent may optionally be used in step 1) of the process for making silyl-terminated polyolefins. The solvent may be a hydrocarbon solvent, such as an aromatic solvent or an isoparaffinic hydrocarbon solvent. Suitable solvents include, but are not limited to, non-polar aliphatic or aromatic hydrocarbon solvents selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, decalin, benzene, toluene, xylene, isoparaffinic fluids including, but not limited to, Isopar™ E, Isopar™ G, Isopar™ H, Isopar™ L, Isopar™ M, dearomatized fluids including, but not limited to, Exxsol™ D or isomers, and mixtures of two or more thereof. Alternatively, the solvent may be toluene and / or Isopar™ E.

[0021] Alternatively, the starting material A), the silyl-terminated polyolefin, can have two silyl-terminated groups per molecule (i.e., in formulas (A2) and (A3) where subscript f=0, the silyl-terminated polyolefin is telechelic). Such telechelic silyl-terminated polyolefins can be prepared by methods such as those disclosed in co-pending U.S. Patent Application Serial No. 62 / 644,808, filed March 19, 2018, which is incorporated herein by reference. Telechelic silyl-terminated polyolefins can be prepared, for example, by a process comprising: 1) combining starting materials comprising a') a silicon-terminated organometallic and c) a halosilane (as described above), thereby obtaining a product comprising a silyl-terminated polyolefin. In a further embodiment, the starting material for this process may further comprise b) a nitrogen-containing heterocycle (as described above). The starting material for this process may optionally further comprise d) a solvent (as described above).

[0022] The process may optionally include one or more additional steps. For example, the process may further include 2) recovering the telechelic silyl-terminated polyolefin. Recovery may be carried out by any suitable means, such as precipitation and filtration, optionally with water washing, to remove unwanted materials.

[0023] The amount of each starting material depends on various factors, including the specific selection of each starting material. However, in certain embodiments, a molar excess of starting material c) may be used per molar equivalent of starting material a'). For example, the amount of starting material c) may be 2 to 3 molar equivalents per molar equivalent of starting material a'). When starting material b) is used, the amount of starting material b) may be 2 molar equivalents per molar equivalent of starting material a').

[0024] The amount of d) solvent depends on various factors, including the selection of starting materials a'), c), and, if present, b). However, the amount of d) solvent may be 65%-95% based on the total weight of all starting materials used in step 1).

[0025] The starting material a') is a compound of formula (II) or (III): [ka] and may be a silicon-terminated organometallic having the formula: MA is a divalent metal selected from the group consisting of Zn, Mg, and Ca; Mb is a trivalent metal selected from the group consisting of Al, B, and Ga; each Z is an independently selected divalent hydrocarbyl group of 1 to 20 carbon atoms; m is a number between 1 and 100,000; each J is independently a hydrogen atom or a monovalent hydrocarbyl group of 1 to 20 carbon atoms; Each R A , R B , and R Care independently a hydrogen atom, a monovalent hydrocarbyl group of 1 to 10 carbon atoms, a vinyl group, an alkoxy group, or M, D and T units: [ka] wherein each R is independently a hydrogen atom, a monovalent hydrocarbyl group of 1 to 10 carbon atoms, or a cyclic, vinyl, or alkoxy group; R A , R B , and R C are each independently one or more siloxy units selected from D and T units, R A , R B , and R C Two or all three of may optionally be linked together to form a ring structure.

[0026] In certain embodiments, the subscript m in formulas (II) and (III) is a number between 1 and 75,000, between 1 and 50,000, between 1 and 25,000, between 1 and 10,000, between 1 and 5,000, between 1 and 2,500, and / or between 1 and 1,000.

[0027] In certain embodiments of Formula (II), MA is Zn. In certain embodiments of Formula (III), MB is Al. In a further embodiment of Formula (II), J is an ethyl group. In a further embodiment of Formula (III), J is a hydrogen atom.

[0028] Prior to this process, silicon-terminated organometallics can be prepared according to the disclosures in co-pending U.S. patent applications Ser. Nos. 62 / 644654 and 62 / 644664, filed Mar. 19, 2018, both of which are incorporated herein by reference.

[0029] For example, in certain embodiments, silicon-terminated organometallics can be prepared by a process comprising combining starting materials including (a) a vinyl-terminated silicon-based compound, (b) a chain shuttling agent, (c) a procatalyst, (d) an activator, (e) an optional solvent, and (f) an optional scavenger, thereby obtaining a product comprising a silicon-terminated organometallic.

[0030] Alternatively, silicon-terminated organometallics may be prepared by a process comprising combining starting materials at elevated temperatures, the starting materials comprising (a) a vinyl-terminated silicon-based compound, (b) a chain shuttling agent, and optionally (e) a solvent. The process may be carried out at temperatures between 60°C and 200°C, alternatively between 80°C and 180°C, and alternatively between 100°C and 150°C. The process may be carried out for a period of 30 minutes to 200 hours.

[0031] In certain embodiments, (a) the vinyl-terminated silicon-based compound has formula (IV): [ka] (In the formula, Z, R A , R B , and R C is as described above).

[0032] In certain embodiments, (b) the chain shuttling agent has the formula R F N M, wherein R F , M, and subscript N are as above.

[0033] In certain embodiments, (c) the procatalyst may be any compound or combination of compounds capable of polymerizing unsaturated monomers when combined with an activator. Suitable procatalysts include, but are not limited to, those disclosed in WO2005 / 090426, WO2005 / 090427, WO2007 / 035485, WO2009 / 012215, WO2014 / 105411, WO2017 / 173080, U.S. Patent Application Publication Nos. 2006 / 0199930, 2007 / 0167578, 2008 / 0311812, and U.S. Patent Nos. 7,355,089 B2, 8,058,373 B2, and 8,785,554 B2. The nitrogen-containing heterocycle and halosilane are as described above for the starting materials b) and c) used to make the silyl-terminated polyolefin having one terminal silyl group per molecule.

[0034] In certain embodiments, (d) the activator may be any compound or combination of compounds capable of activating the procatalyst to form an active catalyst composition or system. Suitable activators include, but are not limited to, Bronsted acids, Lewis acids, carbocation species, or any activators known in the art, such as those disclosed in WO 2005 / 090427 and U.S. Pat. No. 8,501,885 B2. In an exemplary embodiment, the cocatalyst is a catalyst having a carboxyl group selected from the group consisting of [(C 16-18 H 33-37 )2CH3NH]tetrakis(pentafluorophenyl)borate salt.

[0035] In certain embodiments, (e) the optional solvent may be any solvent as disclosed above or described below as starting material (d).

[0036] In a further embodiment, the silicon-terminated organometallic prepared by the above process may be followed by a subsequent polymerization step. Specifically, the silicon-terminated organometallic prepared by the above process may be combined with at least one olefin monomer, a procatalyst as defined herein, an activator as defined herein, and optional materials such as a solvent and / or scavenger under polymerization process conditions known in the art, including but not limited to those disclosed in U.S. Patent Nos. 7,858,706 and 8,053,529. Such a polymerization step essentially increases the subscript n in formula (I) and the subscript m in formulas (II) and (III). Examples of olefin monomers suitable for use in the polymerization step are listed above.

[0037] As described below, silicon-terminated organometallics can also be prepared by combining starting materials including 6-bromo-1-hexene, THF, and chlorodimethylsilane to form hex-5-en-1-yldimethylsilane, followed by combining hex-5-en-1-yldimethylsilane, triethylborane, borane-dimethylsulfide complex, and diethylzinc to form the silicon-terminated organometallic.

[0038] Alternatively, silicon-terminated organometallics can be prepared in a batch reactor using a process such as that described in Reference Example H below, by varying the appropriate starting materials, i.e., olefin monomer, catalyst, chain shuttling agent, catalyst, procatalyst, activator, and solvent (suitable examples of which are described herein). Step 1) of combining the starting materials can be carried out by any suitable means, such as mixing at ambient pressure at a temperature of 50°C to 200°C, alternatively 100°C to 120°C. Heating can be carried out under inert, dry conditions. In certain embodiments, step 1) of combining the starting materials can be carried out for a period of 30 minutes to 20 hours, alternatively 1 hour to 10 hours. In further embodiments, step 1) of combining the starting materials can be carried out by solution processing (i.e., (d) dissolving and / or dispersing the starting materials in a solvent and heating) or melt extrusion (e.g., (d) where a solvent is not used or is removed during processing).

[0039] The silicon-terminated organometallic prepared as described above for starting material (a') can then be combined with (c) a halosilane, and optionally (b) a nitrogen-containing heterocycle, and / or (d) a solvent, as described above, thereby producing a telechelic silyl-terminated polyolefin.

[0040] Alternatively, silyl-terminated polyolefins may be prepared by a solution polymerization process, in which polyolefin polymers are made by a method comprising: a) combining i) an olefin monomer, ii) a catalyst, and iii) a chain shuttling agent as described above to prepare iv) a polymeryl metal; and b) combining iv) the polymeryl metal, v) a halosilane, and optionally v) a nitrogen-containing heterocycle, wherein steps a) and b) are carried out in solution. In solution, the resulting silyl-terminated polyolefin may comprise 10% to 20% of the total weight of the reaction mixture. The remainder typically comprises unreacted olefin monomer and non-reactive solvent. Commercial processes are typically carried out in continuous reactors, where fresh olefin monomer and catalyst are continuously fed to achieve steady-state conversion to polyolefin, and polyolefin is removed at a rate commensurate with these feeds and conversion to polyolefin. In these systems, the olefin monomer is not completely converted to polyolefin. For example, in the copolymerization of ethylene and alpha-olefins, the effluent from the reactor typically contains unreacted monomers, 10% ethylene, and more than 50% alpha-olefin. After polymerization, the solvent and unreacted monomers can be removed by a devolatilization process, leaving a solid silyl-terminated polyolefin.

[0041] After devolatilization of the silyl-terminated polyolefin, the starting materials, including the silyl-terminated polyolefin, polydiorganosiloxane, and catalyst, may be combined in step 1) of the above-described method for preparing a polyolefin-polydiorganosiloxane block copolymer. Alternatively, the devolatilization step may be omitted, i.e., the mixture formed after step b) may be used to deliver starting material A) silyl-terminated polyolefin in step 1) of the method described herein. This method for preparing a polyolefin-polydiorganosiloxane block copolymer described herein may offer the advantage that coupling of the polydiorganosiloxane with the silyl-terminated polyolefin may be carried out in the presence of unreacted olefin monomer (e.g., in solution, without devolatilizing the silyl-terminated polyolefin described above). In this type of system, the polydiorganosiloxane could be fed to a second reactor together with the effluent from the above-described continuous reactor for preparing the silyl-terminated polyolefin. Because the chemistry in the second reactor does not involve the reaction of the olefin, it is expected that this can be done in the presence of olefin monomer without adversely affecting coupling efficiency. This represents an advantage over previous processes, in which unreacted monomer from the series reactors presented the challenge of coupling via hydrosilylation in the second reactor before devolatilization. In this previous process, the concentration of free olefin monomer was much higher than the concentration of vinyl-terminated polyolefin, resulting in poor coupling efficiency between the siloxane and polyolefin unless the olefin monomer was removed prior to this second reaction. The present invention offers the advantage of enabling efficient coupling in the second reactor in solution, and the resulting polyolefin-polydiorganosiloxane block copolymer can then be devolatilized.Thus, in one embodiment of the present invention, the method can further include: i) forming A) a silyl-terminated polyolefin as described herein in a mixture of unreacted monomer and, optionally, a solvent; and ii) combining that mixture with B) a substantially linear polydiorganosiloxane as described above; and C) the Lewis acid catalyst of step 1) of the method.

[0042] Starting material A) may be one silyl-terminated polyolefin or may comprise two or more silyl-terminated polyolefins that differ in at least one of the following properties: structure, viscosity, average molecular weight, olefin block, and sequence. Alternatively, starting material A) may comprise a mixture of silyl-terminated polyolefins, where both silyl-terminated polyolefins having one terminal silyl group per molecule (mono-terminated silyl-terminated polyolefins) and telechelic silyl-terminated polyolefins are used in the mixture for starting material A).

[0043] The amount of starting material A) used in step 1) of the methods for making the copolymers described herein depends on various factors, including whether a mixture of mono- and telechelic silyl-terminated polyolefins is used, the desired structure of the polyolefin-polydiorganosiloxane block copolymer to be formed, and the selection of starting material B), but the amount of starting material A) may be 5% to 95% based on the total weight of all starting materials combined in step 1. Alternatively, the amount of starting material A) may be 10% to 60%, and alternatively 10% to 40%, on the same basis.

[0044] B) Polydiorganosiloxane In the method for making the copolymer, starting material B) is a polydiorganosiloxane having one to two hydrolyzable substituents per molecule capable of reacting with silicon-bonded hydrogen atoms of starting material A). The polydiorganosiloxane is substantially linear or alternatively linear.

[0045] The starting material B) may comprise a polydiorganosiloxane of formula (B1): [ka] In the formula, each R 2 are independently hydrolyzable substituents, and each R 3 are independently hydrogen atoms or monovalent organic groups that do not contain hydrolyzable functionality, and R 4 is R 2 and R 3 where subscript b is 0 or a positive number. Alternatively, subscript b has an average value of at least 2. Alternatively, subscript b may be 2 to 2000. Alternatively, subscript b may be 10 to 1,000. Alternatively, subscript b may be 30 to 500.

[0046] R 2 The hydrolyzable substituent for may be any hydrolyzable substituent capable of reacting with a silicon-bonded hydrogen atom of the starting material A). Exemplary hydrolyzable substituents include halogen atoms such as chlorine or iodine; amide groups such as acetamido, benzamido, or methylacetamido; acyloxy groups such as acetoxy; hydrocarbyloxy groups such as alkoxy or alkenyloxy groups; amino groups; aminoxy groups; hydroxyl groups; mercapto groups; oximo groups; ketoximo groups; alkoxysilylhydrocarbylene functional groups; or combinations thereof. Alternatively, each R 2 Alternatively, each R 2 may be selected from alkoxy and hydroxyl groups. Alternatively, each R 2 Alternatively, each R 2 may be a hydroxyl group.

[0047] R 3 Suitable monovalent organic groups include monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups. Examples of monovalent hydrocarbyl groups are, for example, R 1alkyl, such as those described above for R 1 Examples of monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl and 2,3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl. Examples of other monovalent organic groups include, but are not limited to, oxygen-substituted hydrocarbyl groups such as glycidoxyalkyl, and nitrogen-substituted hydrocarbon groups such as aminoalkyl, and cyano-functional groups such as cyanoethyl and cyanopropyl. 3 is a monovalent hydrocarbyl group exemplified by alkyl and aryl, alternatively methyl and phenyl.

[0048] In one embodiment, each R 4 is R as above 3 Alternatively, each R 4 is R as above 2 Alternatively, a mixture of polydiorganosiloxanes may be used as starting material B), with R 4 Some examples of R 3 and R 4 Another example of R 2 The starting material B) may be one polydiorganosiloxane or may comprise two or more polyorganosiloxanes that differ in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units, and sequence.

[0049] The starting material B) is i) α,ω-dimethylhydroxylsiloxy terminated polydimethylsiloxane; ii) α-dimethylhydroxylsiloxy-terminated, ω-trimethylsiloxy-terminated, polydimethylsiloxane; iii) α,ω-dimethylhydroxylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane); iv) α-dimethylhydroxylsiloxy-terminated, ω-trimethylsiloxy-terminated, poly(dimethylsiloxane / methylphenylsiloxane); v) α,ω-(phenyl, methyl, hydroxyl-siloxy) terminated, polydimethylsiloxane; vi) α,ω-dimethylmethoxysiloxy-terminated polydimethylsiloxane; vii) α-dimethylmethoxysiloxy terminated, ω-trimethylsiloxy terminated, polydimethylsiloxane; viii) may include polydiorganosiloxanes such as combinations of two or more of i), ii), iii), iv), v), vi), and vii).

[0050] Methods for preparing polydiorganosiloxanes suitable for use as starting material B) are well known in the art, such as by hydrolysis and condensation of the corresponding organohalosilanes or by equilibration of cyclic polydiorganosiloxanes.

[0051] The amount of starting material B) used in step 1) of the methods described herein depends on various factors, including whether a mixture of mono-terminated and telechelic polydiorganosiloxanes is used, the desired structure of the polyolefin-polydiorganosiloxane block copolymer to be formed, and the selection of starting materials A) and B), but the amount of starting material B) may be 5% to 95% based on the total weight of all starting materials combined in step 1. Alternatively, the amount of starting material B) may be 10% to 60%, and alternatively 10% to 40%, on the same basis.

[0052] C) catalyst In the method for preparing the copolymer, the starting material C) catalyst may be a Lewis acid catalyst. Suitable Lewis acid catalysts include those containing boron. Alternatively, the Lewis acid catalyst may be a trivalent boron compound having at least one perfluoroaryl group, alternatively 1 to 3 perfluoroaryl groups per molecule, alternatively 2 to 3 perfluoroaryl groups per molecule, and alternatively 3 perfluoroaryl groups per molecule. The perfluoroaryl group may have 6 to 12 carbon atoms, alternatively 6 to 10 carbon atoms, and alternatively 6 carbon atoms. For example, Lewis acid catalysts include (C5F4)(C6F5)2B; (C5F4)3B; (C6F5)BF2; BF(C6F5)2; B(C6F5)3; BCl2(C6F5); BCl(C6F5)2; B(C6H5)(C6F5)2; B(C6H5)2(C6F5); [C6H4(mCF3)]3B; [C6H4(pOCF3)]3B; (C6F5)B(OH)2; (C6F5)2BOH; (C6F5)2BH; (C6F5)BH2; (C7H 11 )B(C6F5)2;(C8H 14 )B(C6F5); (C6F5)2B(OC2H5); or (C6F5)2B-CH2CH2Si(CH3). Alternatively, the starting material C) may be a Piers-Rubinsztajn reaction catalyst of formula B(C6F5)3, tris(pentafluorophenyl)borane.

[0053] The amount of catalyst used in step 1) of the methods described herein will depend on various factors, such as the selection of starting materials A) and B) and their respective contents of silicon-bonded hydrogen atoms and hydrolyzable substituents, and the temperature during step 1), but the amount of catalyst is sufficient to catalyze the reaction of the starting materials including A) and B), alternatively, the amount of catalyst is sufficient to provide 0.0001 to 0.1 molar equivalents of catalyst per molar equivalent of hydrolyzable substituents of starting material B), alternatively, 0.001 to 0.1, alternatively, 0.005 to 0.05 molar equivalents on the same basis.

[0054] D) Solvent Starting material D) may optionally be added during the process for preparing the copolymer. The solvent may be an organic solvent, examples of which include D1) a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; D2) an aromatic hydrocarbon such as benzene, toluene, or xylene; D3) an aliphatic hydrocarbon such as heptane, hexane, or octane; D4) a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether; D5) a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride; D6) chloroform; D7) dimethyl sulfoxide; D8) dimethylformamide; D9) acetonitrile; D10) tetrahydrofuran; D11) white spirit; D12) mineral spirits; D13) naphtha; D14) ExxonMobil Chemical Isoparaffins such as Isopar™ E available from the Company, or combinations of two or more of D1), D2), D3), D4), D5), D6), D7), D8), D9), D10), D11), D12), D13), and D14).

[0055] The amount of solvent depends on various factors, including the type of solvent selected and the amount and type of starting materials selected for use in step 1) of the method for preparing polyolefin-polydiorganosiloxane block copolymers described herein. However, if present, the amount of solvent may range from 1% to 99%, alternatively 2% to 50%, based on the total weight of all starting materials combined in step 1). Solvent may be added during the combination of starting materials, including A), B), and C), for example, to aid in mixing and delivery. Alternatively, one or more of the starting materials may be dissolved in a solvent before being combined with the other starting materials in step 1) of the method described herein.

[0056] Starting Materials E) Alkoxysilyl-Functional Organosilicon Compounds Starting material E) is an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom. Examples of suitable alkoxysilyl-functional organosilicon compounds are those having the unit formula (E1): [ka] (HR 3 2SiO 1 / 2 ) dd (R 3 3SiO 1 / 2 ) ee (HR 3 SiO 2 / 2 ) ff (R 3 2SiO 2 / 2 ) gg (R 3 SiO 3 / 2 ) hh (HSiO 3 / 2 ) ii (SiO 4 / 2 ) jj alkoxy-functional organohydrogensiloxane oligomers of the formula: 1 and R 3 is as above, each subscript aa is independently 0, 1, or 2, alternatively 0 or 1, each subscript bb is independently 0, 1, or 2, and subscript cc > 0, and each R D are independently divalent hydrocarbyl groups of 2 to 18 carbon atoms, subscript dd≧0, subscript ee has a value such that 5≧ee≧0, subscript ff≧0, subscript gg≧0, subscript hh>0, subscript ii≧0, and subscript jj≧0, and the quantity (cc+dd+ee+ff+gg+hh+ii+jj)≦50. D Suitable divalent hydrocarbyl groups for are alkylene groups such as ethylene, propylene, butylene or hexylene; arylene groups such as phenylene; or [ka] Alternatively, each R D is a group of the formula -CH-. Examples of such alkoxy-functional organohydrogensiloxane oligomers can be prepared by the methods of U.S. Pat. No. 3,175,993 to Weyenberg and co-pending U.S. Provisional Patent Applications Nos. 62 / 524636, 62 / 524637, and 62 / 524639, all filed June 26, 2017, and all incorporated herein by reference.

[0057] Alternatively, the starting material E) may be of formula (E2): [ka] wherein R 1 , R 3 , R D , and subscript aa is as above, and subscript D is 0-20, alternatively 1-10.

[0058] Alternatively, the starting material E) may be a compound of formula (E3): [ka] wherein R 1 , R 3 , R D , and subscript aa are as above.

[0059] Alternatively, starting material E) may comprise formula (E4), (E5), or both: Equation (E4) is [ka] and Equation (E5) is [ka] where R 1 , R 3 , R D , and subscript aa are as above.

[0060] Alternatively, the starting material E) may have the unit formula (E6): [ka] wherein R 1 , R 3 , R D and subscript aa is as above, subscript E is 0 or more, subscript F is 1 or more, subscript G is 1 or more, and 4≦(E+F+G)≦50.

[0061] In the unit formula (I) of the polyolefin-polydiorganosiloxane block copolymers described herein, the group R 10 is formed as a reaction product of silicon-bonded hydrogen atoms of starting material E) and hydrolyzable substituents of starting material B). When starting material E) is included, starting material B) comprises a telechelic polydiorganosiloxane. The amounts of starting materials B) and E) can be selected so that there are up to 1.05 molar equivalents of starting material E) for each molar equivalent of hydrolyzable substituents in the telechelic polydiorganosiloxane for starting material B) (E:B molar ratio). Alternatively, for example, when a triblock copolymer having a BAB structure is formed, the E:B molar ratio can be 1.05:1 to 1:1. In one embodiment, starting materials A), B), C), and E) can be combined simultaneously in step 1). Alternatively, starting materials A), B), and C) may be combined in amounts such that one hydrolyzable substituent (from starting material B) remains unreacted with the SiH from starting material A) at the end of the polyolefin-polydiorganosiloxane block copolymer, and then starting material E) is added such that the SiH on starting material E) reacts with the remaining hydrolyzable substituent from starting material B. In this manner, copolymers having a BAB structure containing alkoxy-silylhydrocarbylene functional end groups, or copolymers having a B(AB)n structure, can be prepared.

[0062] The polyolefin-polydiorganosiloxane block copolymers prepared as described above have the unit formula (I): [ka] wherein R 1 , R 3 , subscript a, and subscript b are as above.

[0063] Each R 5 are independently selected hydrogen-terminated polyolefin blocks. 5 is the unit formula H[(R et ) t (R O ) u ] g wherein R et , R O , and the subscripts t, u, and g are as above. Alternatively, each R 5 is the unit formula (II): H[(CH2CH2) t (CHR 7 CH2) u ] g wherein R 7 and the subscripts t, u, and g are as defined above. Alternatively, the hydrogen-terminated polyolefin block may be a hydrogen-terminated ethylene polymer block. Alternatively, the dihydric polyolefin block may be a hydrogen-terminated ethylene-octene copolymer block.

[0064] Each R 6 are independently selected divalent polyolefin blocks. 6 is the unit formula [(R et ) t (R O ) u ] g wherein R et , R O , and the subscripts t, u, and g are as above. Alternatively, each R 6 is a unit of formula (III): [(CH2CH2) t (CHR 7 CH2)u ] g wherein R 7 and the subscripts t, u, and g are as defined above. Alternatively, the divalent polyolefin block may be a divalent ethylene polymer block. Alternatively, the divalent polyolefin block may be a divalent ethylene-octene copolymer block.

[0065] Each R 10 is R 3 and an alkoxysilyl-functional hydrocarbylene-containing group. In one embodiment, each R 10 is R 3 (i.e., when starting material E) is not used to prepare a polyolefin-polydiorganosiloxane block copolymer). Alternatively, R 10 At least some examples of: [ka] [ka] wherein R 1 , R 3 , R D , and subscripts aa, D, E, F, and G are as above.

[0066] In the above unit formula (I), the subscript w is 0 to 2. The subscript x is 0 or a positive number. The subscript y is 0 or a positive number. The subscript z is 0 to 2. The quantity (w+y)≧1, the quantity (x+z)≧1. If the subscript w=0, then the subscript z is >0. If the subscript z=0, then the subscript w>0.

[0067] In one embodiment, in unit formula (I), subscript x=0, subscript y=0, subscript w=1, and subscript z=1. In this embodiment, the polyolefin-polydiorganosiloxane block copolymer has an AB structure. In this embodiment, the copolymer has formula (IV): [ka] wherein R 1 , R 3 , R 5 , R 10 , subscript a, and subscript b are as above.

[0068] In an alternative embodiment, in unit formula (I), subscript w=2, subscript z=0, subscript x≧1, and subscript y≧0. In this embodiment, the copolymer has formula (V): [ka] wherein R 1 , R 3 , R 5 , R 6 , subscript a, and subscript b are as defined above, and subscript c is 0 or a positive number. Alternatively, subscript c may be 1 to 1,000; alternatively 2 to 1,000; alternatively 1 to 100, and alternatively 2 to 100. Alternatively, in formula (V), subscript c>0, i.e., for unit formula (I), subscript w=2, subscript x>1, subscript y>1, and subscript z=0. Alternatively, when subscript c=0, the copolymer has an (ABA) structure.

[0069] In an alternative embodiment, in unit formula (I), subscript w=2, subscript x=1, subscript y=0, and subscript z=0, and the copolymer has an (ABA) structure. The copolymer has formula (VI): [ka] wherein R 1 , R 3 , R 5, subscript a, and subscript b are as above. This copolymer can be made by the above method where starting material A) has one silyl terminal group per molecule and starting material B) has two hydrolyzable substituents per molecule (telechelic).

[0070] In an alternative embodiment, in unit formula (I), subscript z=2, subscript w=0, subscript x≧0, and subscript y≧1, and the copolymer has formula (VII): [ka] wherein R 1 , R 3 , R 6 , R 10 , subscript a, and subscript b are as defined above, and subscript d is 0 or a positive number. Alternatively, subscript d may be 1 to 1,000; alternatively 2 to 1,000; alternatively 1 to 100, and alternatively 2 to 100. Alternatively, in formula (VII), subscript d>0, i.e., for unit formula (I), subscript w=0, subscript x>1, subscript y>1, and subscript z=2. Alternatively, subscript d=0, and the copolymer has a (BAB) structure.

[0071] In an alternative embodiment, in unit formula (I), subscript w=0, subscript x=1, subscript y=0, and subscript z=2, and the copolymer has formula (VIII): [ka] wherein R 1 , R 3 , R 6 , R 10 , subscript a, and subscript b are as above. This copolymer can be made by the above method where starting material B) has one hydrolyzable substituent per molecule and starting material A) is telechelic.

[0072] Alternatively, any one of formulas (I) and (IV)-(VIII) may include: each R 1 is methyl, and each R 3 and R is methyl. In this embodiment, each R 5 may be hydrogen-terminated polyethylene or hydrogen-terminated poly(ethylene / octene), and each R 6 may be polyethylene or poly(ethylene / octene). Any one or more of the polyolefin-polydiorganosiloxane copolymers prepared as described above may be used as the starting material (A) in a hot melt adhesive composition.

[0073] B) Polydiorganosiloxane The polydiorganosiloxanes useful as starting material (B) in the hot melt adhesive composition may be substantially linear, or alternatively may be linear. The polydiorganosiloxanes may be of the formula X 3 kk R 3 (2-kk) SiO 2 / 2 and a difunctional unit ("D" unit) of formula X 3 mm R M (3-mm) SiR L1 wherein each R M are independently selected monovalent organic groups, e.g., R 3 As mentioned above, each X 3 are independently selected hydrolyzable substituents, the subscript kk is 0 or 1, the subscript mm is 0, 1, or 2, and R L1 is an oxygen atom or a divalent hydrocarbyl group that links a silicon atom of a terminal unit to another silicon atom. Polydiorganosiloxanes are those having the formula R M SiO 3 / 2 may optionally contain up to 20% based on the total trifunctional units ("T" units) of the formula M is as above.

[0074] Alternatively, in (B) polydiorganosiloxane, each R M may be independently selected from the group consisting of alkyl, alkenyl, and aryl. Alternatively, each R M may be selected from methyl, vinyl, and phenyl. Alternatively, R M At least 50%, or alternatively at least 80%, of the groups are alkyl groups of 1 to 4 carbon atoms or methyl groups. Alternatively, the terminal units of the polydiorganosiloxane are (MeSiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (Me2ViSiO 1 / 2 ), and the D units can be exemplified by (MeSiO 2 / 2 ) and (MePhSiO 2 / 2 ) can be exemplified by:

[0075] In the formula for the terminal unit, R L1 R is an oxygen atom, a divalent hydrocarbyl group, or a combination of a divalent hydrocarbyl group and a divalent siloxane group. L1 R bonds the silicon atom of the terminal unit to another silicon atom in the polydiorganosiloxane so that the terminal unit is not removed during solidification of the hot melt adhesive composition. L1 Suitable divalent hydrocarbyl groups for are alkylene groups such as ethylene, propylene, butylene or hexylene; arylene groups such as phenylene; or [ka] Alternatively, R L1 An example of R may be an oxygen atom, L1 A different example of R is a divalent hydrocarbyl group. Alternatively, each R L1 R may be an oxygen atom. L1When is a divalent hydrocarbyl group, starting material (B) may comprise the reaction product of an alkoxysilane-functional organosiloxane compound having at least one silicon-bonded hydrogen atom with an average of at least two aliphatically unsaturated organic groups per molecule in the presence of a hydrosilylation catalyst.

[0076] X 3 Examples of hydrolyzable substituents for X include hydrogen atoms, halogen atoms, amide groups such as acetamido, benzamido, or methylacetamido groups, acyloxy groups such as acetoxy groups, hydrocarbyloxy groups such as alkoxy groups (e.g., methoxy and ethoxy) or alkenyloxy groups, amino groups, aminoxy groups, hydroxyl groups, mercapto groups, oximo groups, ketoximo groups, alkoxysilylhydrocarbylene functional groups, or combinations thereof. Alternatively, X 3 may be selected from a halogen atom; an amide group such as an acetamido group, a benzamido group, or a methylacetamido group; an acyloxy group such as an acetoxy group; a hydrocarbyloxy group such as an alkoxy group (e.g., methoxy and ethoxy) or an alkenyloxy group; an amino group; an aminoxy group; a hydroxyl group; a mercapto group; an alkoxysilylhydrocarbylene group; or a combination thereof. Alternatively, each X may be a hydroxyl group, a hydrocarbyloxy group, or an alkoxysilylhydrocarbylene group. Alternatively, each X 3 may be a hydroxyl group or a methoxy group. Alternatively, each X may be a hydroxyl group. Alternatively, each X 3 may be an alkoxysilylhydrocarbylene group.

[0077] In one embodiment, the polydiorganosiloxane may have a hydrolyzable substituent, i.e., at least one of the subscripts kk and mm is >0. In this embodiment, the hot melt adhesive composition may be reactive, e.g., condensation-curable. Suitable polydiorganosiloxanes with hydrolyzable substituents for starting material (B) are disclosed, for example, in U.S. Pat. No. 8,580,073, column 4, line 35 to column 5, line 56.

[0078] In this embodiment, the starting material (B) has the formula (B1): [ka] wherein R L1 , R M , and X 3 is as above, each subscript nn is independently 1, 2, or 3, and the subscript oo is an integer having a value sufficient to provide, for the polydiorganosiloxane, a zero-shear viscosity of at least 1000 mPa·s at 25°C and / or a DP of at least 300. DP can be measured by GPC using a polystyrene standard calibration. Alternatively, the subscript oo can have a value in the range of 100 to 10,000. Such viscosity measurements can be performed using a rheometer equipped with a cone-and-plate geometry, and the zero-shear viscosity is obtained in a situation where the viscosity is independent of shear stress and shear rate.

[0079] Alternatively, starting material (B) may be a compound represented by formula (B1) above, where each subscript nn is 1 and each R L1 When is an oxygen atom, the starting material (B) may comprise an α,ω-difunctional polydiorganosiloxane. For example, the starting material (B) may comprise a polydiorganosiloxane having the formula (B2): X 3 R M 2SiO-(R M 2SiO) pp -SiR M 2X 3 wherein X3 and R M is as defined above, and the subscript pp is an integer having a value sufficient to impart the above-described viscosity to the polydiorganosiloxane of formula (B2). Alternatively, the subscript pp may have a value ranging from 100 to 10,000, alternatively from 150 to 500, and alternatively from 300 to 900.

[0080] Alternatively, starting material (B) may comprise a hydroxyl-functional polydiorganosiloxane of formula (B2) above, wherein each X 3 may be a hydroxyl group, and each R M may be an alkyl group such as methyl, and the subscript pp may have a value such that the hydroxyl-functional polydiorganosiloxane has a zero-shear viscosity of at least 1000 mPa·s at 25°C. Alternatively, the subscript pp value may have a value ranging from 300 to 900. An exemplary hydroxyl-endblocked polydiorganosiloxane is a hydroxyl-endblocked polydimethylsiloxane. Silanol-endblocked polydiorganosiloxanes suitable for use as starting material (B) can be prepared by methods known in the art, such as the hydrolysis and condensation of the corresponding organohalosilanes or the equilibration of cyclic polydiorganosiloxanes.

[0081] Alternatively, the starting material (B) may be, for example, a compound represented by the formula (B1) above, where each R L1 When R is a divalent hydrocarbyl group or a combination of divalent hydrocarbyl and divalent siloxane groups, it may comprise an alkoxysilylhydrocarbylene endblocked polydiorganosiloxane. M may be alkyl, and each R L1 may be an alkylene such as ethylene, and each subscript nn may be 3.

[0082] Alkoxysilylhydrocarbylene end-blocked polydiorganosiloxanes can be prepared by reacting vinyl-terminated polydimethylsiloxanes with (alkoxysilylhydrocarbyl)tetramethyldisiloxanes. Examples of such alkoxysilylhydrocarbylene end-blocked polydiorganosiloxanes can be prepared by methods such as those disclosed in U.S. Patent No. 3,175,993 to Weyenberg, and in U.S. Patent Publication No. 2015 / 0376482, paragraphs

[0016] to

[0020] and

[0045] to

[0060] , both of which are incorporated herein by reference. Alternatively, R 3 However, polydiorganosiloxanes containing divalent hydrocarbon groups can be prepared by reacting the above-described polydiorganosiloxanes having terminal aliphatic unsaturation groups with an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom at the end of the molecule in the presence of a hydrosilylation catalyst, such as the catalyst described below. Examples of suitable alkoxysilyl-functional organosilicon compounds have the unit formula: [ka] (HR 3 2SiO 1 / 2 ) dd (R 3 3SiO 1 / 2 ) ee (HR 3 SiO 2 / 2 ) ff (R 3 2SiO 2 / 2 ) gg (R 3 SiO 3 / 2 ) hh (HSiO 3 / 2 ) ii (SiO 4 / 2 ) jj and is exemplified by an alkoxy-functional organohydrogensiloxane oligomer of the formula: 1 and R 3and the subscripts aa, bb, cc, dd, ee, ff, gg, hh, ii, and jj are as defined above. Examples of such alkoxy-functional organohydrogensiloxane oligomers can be prepared by the methods of co-pending U.S. Provisional Patent Applications Nos. 62 / 524636, 62 / 524637, and 62 / 524639, all filed June 26, 2017, and all incorporated herein by reference.

[0083] Alternatively, the (B) polydiorganosiloxane may be free of hydrolyzable substituents if the subscript kk=0 and the subscript mm=0 in the D units and terminal units above. In one embodiment, for example, if the hot melt adhesive composition is hydrosilylation reaction curable, the polydiorganosiloxane may have terminal aliphatic unsaturated groups.

[0084] In this embodiment, the starting material (B) is Formula (B3):R M1 2nd Round M2 SiO(R M1 2SiO) qq (R M1 R M2 SiO) rr SiR M1 2nd Round M2 , Formula (B4):R M1 3SiO(R M1 2SiO) ss (R M1 R M2 SiO) tt SiR M1 3. or a combination thereof.

[0085] In formulas (B3) and (B4), each R M1 are independently monovalent hydrocarbyl groups containing no hydrogen atoms or aliphatic unsaturation, and each R M2are independently aliphatically unsaturated hydrocarbyl groups. The subscript qq can be 0 or a positive number. Alternatively, the subscript qq has an average value of at least 2. Alternatively, the subscript qq may have a value in the range of 2 to 2000. The subscript rr can be 0 or a positive number. Alternatively, the average value of the subscript rr may be in the range of 0 to 2000. The subscript ss can be 0 or a positive number. Alternatively, the subscript ss may have an average value in the range of 0 to 2000. The subscript tt has an average value of at least 2. Alternatively, the subscript tt may have an average value in the range of 2 to 2000. R M1 Suitable monovalent organic groups for are as described above. Alternatively, in formulas (B3) and (B4), each R M1 is a monovalent hydrocarbon radical exemplified by alkyl such as methyl and aryl such as phenyl, and each R M2 are independently aliphatically unsaturated monovalent organic groups exemplified by alkenyl groups such as vinyl, allyl, butenyl, and hexenyl, and alkynyl groups such as ethynyl and propynyl.

[0086] In this embodiment, the starting material (B) is a polydiorganosiloxane, such as i) dimethylvinylsiloxy-terminated polydimethylsiloxane; ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane; iv) trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); v) trimethylsiloxy-terminated polymethylvinylsiloxane; vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane); ix) phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxanes; x) dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane; xiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xiv) Trimethylsiloxy-terminated polymethylhexenylsiloxane xv) dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / methylhexenylsiloxane), xvi) Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane) xvii) polydiorganosiloxanes, such as combinations thereof.

[0087] Methods for preparing polydiorganosiloxanes suitable for use as starting material (B), such as by hydrolysis and condensation of the corresponding organohalosilanes or by equilibration of cyclic polydiorganosiloxanes, are well known in the art. In an alternative embodiment, the polydiorganosiloxane has the formula (B5): R M3 3SiO(R M3 2SiO) ss SiR M3 3, where the subscript ss is as defined above, and each R M3 are independently selected monovalent hydrocarbyl groups free of aliphatic unsaturation. M3 can be an alkyl group or an aryl group such as phenyl. Alternatively, each R M3 can be an alkyl group such as methyl.

[0088] The polydiorganosiloxanes of formula (B5) may be used in non-reactive hot melt adhesive compositions or may contain reactive substituents (e.g., hydrolyzable substituents X for condensation reaction curable hot melt adhesive compositions, or for polydiorganosiloxanes with terminal aliphatic unsaturated hydrocarbyl groups in hydrosilylation curable hot melt adhesive compositions). 3 (B5) may be added to a reactive hot melt adhesive composition containing one or more additional polydiorganosiloxanes having the formula (B6). Examples of polydiorganosiloxanes of formula (B7) include trimethylsiloxy-terminated polydimethylsiloxanes and trimethylsiloxy-terminated (dimethyl / methylphenyl)siloxane copolymers.

[0089] The amount of starting material (B) in the hot melt adhesive composition will depend on various factors, including whether any starting materials are added in addition to (A), (B), and (C), and whether the hot melt adhesive composition is reactive. However, starting material (B) polydiorganosiloxane may be present in the hot melt adhesive composition in an amount of 0% to 35%, based on the total weight of all starting materials in the hot melt adhesive composition, or alternatively, in an amount of 5% to 25% on the same basis.

[0090] (C) Polyorganosilicate resin The polyorganosilicate resin (C) useful as a starting material is represented by the formula R M 3SiO 1 / 2の monofunctional units ("M" units) and a group of formula SiO 4 / 2 and tetrafunctional silicate units ("Q" units) of the formula M are independently selected monovalent organic groups, as described above for starting material (B). Alternatively, in the polyorganosilicate resin, each R M may be independently selected from the group consisting of alkyl, alkenyl, and aryl. Alternatively, each R M may be selected from methyl, vinyl, and phenyl. Alternatively, R MAt least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M units are (MeSiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (Me2ViSiO 1 / 2 The polyorganosilicate resins are soluble in solvents such as those listed above, exemplified by liquid hydrocarbons such as benzene, toluene, xylene, and heptane, or in liquid organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0091] Once prepared, the polyorganosilicate resin contains the M and Q units described above, and the polyorganosiloxane further contains units having silicon-bonded hydroxyl groups, and has the formula Si(OSiR M 3) may contain a neopentamer of 4, where R M is as described above, and for example, the neopentamer may be tetrakis(trimethylsiloxy)silane. 29 Si NMR spectroscopy can be used to measure the hydroxyl content and the molar ratio of M and Q units, which is expressed as {M(resin)} / {Q(resin)}, excluding the M and Q units from the neopentamer. The M:Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M units) in the resin portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resin portion. The M:Q ratio is between 0.5:1 and 1.5:1.

[0092] The Mn of the polyorganosilicate resin is determined by the R M The Mn of the polyorganosilicate resins depends on various factors, including the type of hydrocarbon group represented by the formula (Mn). The Mn of the polyorganosilicate resins refers to the number average molecular weight measured using gel permeation chromatography (GPC) when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resins may be greater than 3,000 Da, or alternatively, may be >3,000 Da to 8,000 Da. Alternatively, the Mn of the polyorganosilicate resins may be 3,500 Da to 8,000 Da.

[0093] U.S. Patent No. 8,580,073, column 3, line 5 to column 4, line 31, and U.S. Patent Publication No. 2016 / 0376482, paragraphs

[0023] -

[0026] , are incorporated herein by reference to disclose MQ resins, which are suitable polyorganosilicate resins for use in the hot melt adhesive compositions disclosed herein. The polyorganosilicate resins can be prepared by any suitable method, such as cohydrolysis of the corresponding silanes, or by a silica hydrosol capping process. The polyorganosilicate resins can be prepared by a silica hydrosol capping process, such as the processes disclosed in U.S. Patent No. 2,676,182 to Daudt et al., U.S. Patent No. 4,611,042 to Rivers-Farrell et al., and U.S. Patent No. 4,774,310 to Butler et al. The method of Daudt et al., mentioned above, involves reacting a silica hydrosol with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a mixture thereof under acidic conditions, and recovering a copolymer having M- and Q-units. The resulting copolymer generally contains 2 to 5 weight percent hydroxyl groups.

[0094] The intermediates used to prepare the polyorganosilicate resins may be triorganosilanes and silanes or alkali metal silicates having four hydrolyzable substituents. The triorganosilanes have the formula R M 3SiX 1 wherein R M is as above, and X 1 is X 3 represents hydrolyzable substituents such as those listed above for silanes having four hydrolyzable substituents, and the silanes having four hydrolyzable substituents are represented by the formula SiX 2 Each X can have 4 2 is halogen, alkoxy, or hydroxyl. Suitable alkali metal silicates include sodium silicate.

[0095] The polyorganosilicate resins prepared as described above typically contain silicon-bonded hydroxyl groups, i.e., the formula HOSi 3 / 2 and / or HOR M 2SiO 1 / 2 The polyorganosilicate resin may contain up to 2% silicon-bonded hydroxyl groups as measured by FTIR spectroscopy. In certain applications, it may be desirable for the amount of silicon-bonded hydroxyl groups to be less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, or alternatively between 0.3% and 0.8%. The silicon-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin can be converted to trihydrocarbylsiloxane groups or other hydrolyzable groups by reacting the silicone resin with a silane, disiloxane, or disilazane containing the appropriate terminal group. The silane containing the hydrolyzable group may be added in molar excess over the amount required to react with the silicon-bonded hydroxyl groups on the polyorganosilicate resin.

[0096] In one embodiment, the polyorganosilicate resin has the formula XSiO 3 / 2 and / or XR M 2SiO 1 / 2 and optionally 0.3% to 0.8% of units represented by the formula: M is as above, and X is X 3 represents a hydrolyzable substituent, as described above for ##STR00002## The concentration of silanol groups present in the polyorganosiloxane can be determined using FTIR spectroscopy.

[0097] Alternatively, the polyorganosilicate resin may have terminal aliphatic unsaturation. The polyorganosilicate resin may be prepared by reacting the product of Daudt et al. with an end-blocking agent containing unsaturated organic groups and an end-blocking agent free of aliphatic unsaturation in an amount sufficient to provide 3 to 30 mole percent unsaturated organic groups in the final product. Examples of end-blocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable end-blocking agents are known in the art and are exemplified in U.S. Patent Nos. 4,584,355, 4,591,622, and 4,585,836. The resin may be prepared using a single end-blocking agent or a mixture of such agents.

[0098] Alternatively, the polyorganosilicate resin may further comprise an alkoxy functional group. This resin can be prepared by reacting the polyorganosilicate resin having the above-mentioned terminal aliphatic unsaturated groups with an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom at the molecular end in the presence of a hydrosilylation catalyst, such as the catalyst described below. Examples of suitable alkoxysilyl-functional organosilicon compounds include those having the unit formula: [ka] (HR 3 2SiO 1 / 2 ) dd (R 3 3SiO 1 / 2 ) ee (HR 3 SiO 2 / 2 ) ff (R 3 2SiO 2 / 2 ) gg (R 3 SiO 3 / 2 ) hh (HSiO 3 / 2 ) ii (SiO 4 / 2 ) jj and is exemplified by an alkoxy-functional organohydrogensiloxane oligomer of the formula: 1 and R 3and the subscripts aa, bb, cc, dd, ee, ff, gg, hh, ii, and jj are as defined above. Examples of such alkoxy-functional organohydrogensiloxane oligomers can be prepared by the methods of co-pending U.S. Provisional Patent Applications Nos. 62 / 524636, 62 / 524637, and 62 / 524639, all filed June 26, 2017, and all incorporated herein by reference. Examples of polyalkoxysilyl-functional polyorganosilicate resins and methods for their preparation are disclosed, for example, in U.S. Pat. No. 9,862,867 to Gordon et al. and U.S. Patent Publication No. 2015 / 0376482 to Bekemeier et al., paragraphs

[0011] -

[0016] and

[0021] -

[0044] , which are incorporated herein by reference. The resulting polyalkoxysilyl-functional polyorganosilicate resin can be an MQ or MDQ resin.

[0099] The amount of starting material (C) in the hot melt adhesive composition depends on various factors, including whether any starting materials are added in addition to (A), (B), and (C), and whether the hot melt adhesive composition is reactive. However, the starting polyorganosilicate resin (C) can be present in the hot melt adhesive composition in an amount sufficient to provide a weight ratio of (C) polyorganosilicate resin to polydiorganosiloxane (resin / polymer) of 50 / 50 to 70 / 30, alternatively 55 / 45 to 65 / 35. The amount of polydiorganosiloxane in the resin / polymer ratio includes the (B) polydiorganosiloxane and the polydiorganosiloxane blocks of starting material (A).

[0100] (D)Catalyst The catalyst may be any catalyst capable of catalyzing reactive substituents on other starting materials if the hot melt adhesive composition is reactive. If the hot melt adhesive composition is reactive via a hydrosilylation reaction, the catalyst is a hydrosilylation catalyst. If the hot melt adhesive composition is reactive via a condensation reaction, the catalyst is a condensation catalyst. In dual-cure hot melt adhesive compositions, both a hydrosilylation catalyst and a condensation catalyst may be added to the hot melt adhesive composition.

[0101] Hydrosilylation catalysts include platinum group metal catalysts known in the art and commercially available. Such hydrosilylation catalysts may be metals selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation catalyst may be a compound of such a metal, such as chloride tris(triphenylphosphane)rhodium(I) (Wilkinson's catalyst), rhodium diphosphine chelates, such as [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, platinum dichloride, and complexes of these compounds with low molecular weight organopolysiloxanes, or platinum group compounds microencapsulated in a matrix or core-shell structure. Complexes of platinum with low molecular weight organopolysiloxanes include platinum complexes with 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst). These complexes can be microencapsulated in a resin matrix. Alternatively, the hydrosilylation catalyst may include platinum complexes with 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane. Exemplary hydrosilylation catalysts are described in U.S. Pat. Nos. 3,159,601, 3,220,972, 3,296,291, 3,419,593, 3,516,946, 3,814,730, 3,989,668, 4,766,176, 4,784,879, 5,017,654, 5,036,117, and 5,175,325, and EP 0 347 895 B.

[0102] The amount of catalyst used in the hydrosilylation-reactive hot melt adhesive composition depends on various factors, including the selection of starting materials (A), (B), and (C), their respective content of silicon-bonded hydrogen atoms and terminal aliphatic unsaturated groups, whether inhibitors are present, and the processing temperature. However, the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of reactive substituents in the starting materials; alternatively, the amount of catalyst is sufficient to provide 1 ppm to 1000 ppm of platinum group metal, based on the total weight of all starting materials in the hot melt adhesive composition, or alternatively, sufficient to provide 5 ppm to 100 ppm of platinum group metal, based on the same basis.

[0103] Condensation reaction catalysts include tin and titanium compounds that are known in the art and commercially available. Organotin compounds for condensation reaction catalysts are those in which the tin valency is +4 or +2, i.e., tin(IV) compounds or tin(II) compounds. Examples of tin(IV) compounds include stannic salts of carboxylic acids, such as dibutyltin dilaurate, dimethyltin dilaurate, di-(n-butyl)tin bisketonate, dibutyltin diacetate, dibutyltin maleate, dibutyltin diacetylacetonate, dibutyltin dimethoxide, carbomethoxyphenyltin trisuberate, dibutyltin dioctanoate, dibutyltin diformate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineodeconoate, dibutyltin dineodeconoate, triethyltin tartrate, dibutyltin dibenzoate, butyltin tri-2-ethylhexanoate, dioctyltin diacetate, tin octylate, tin oleate, tin butyrate, tin naphthenate, dimethyltin dichloride, combinations thereof, and / or partial hydrolysis products thereof. Tin(IV) compounds are known in the art and are commercially available from Acima Specialty Chemicals of Switzerland, Europe, a business unit of The Dow Chemical Company, such as Metatin™ 740 and Fascat™ 4202. Examples of tin(II) compounds include tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, tin(II) dilaurate, stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, stannous stearate, stannous naphthenate, stannous hexanoate, stannous succinate, stannous caprylate, and combinations thereof. Organotitanium compounds such as tetrabutyl titanate, 2,5-di-isopropoxy-bis(ethyl acetate)titanium, and partially chelated derivatives of these salts with chelating agents such as acetoacetic esters and beta-diketones may alternatively be used as condensation reaction catalysts.

[0104] The amount of catalyst used in the condensation-reactive hot melt adhesive composition depends on various factors, including the selection and type of starting materials (A), (B), and (C), the content of hydrolyzable substituents, whether a crosslinker is present, and the temperature during processing, but the amount of catalyst is sufficient to catalyze the condensation reaction of the reactive substituents in the starting materials. Alternatively, the amount of catalyst may be 0.01% to 3% based on the combined weight of starting materials (A), (B), and (C). Alternatively, the amount of catalyst may be 0.05% to 1% on the same basis.

[0105] (E) Crosslinking agent The starting material (E) is a crosslinking agent, which, when reactive, may be added to the hot melt adhesive composition. The choice of crosslinking agent depends on the type of reactivity, for example, hydrosilylation or condensation, or dual cure.

[0106] In one embodiment, for example, when the hot melt adhesive composition is hydrosilylation reactive, the crosslinker can be a silyl compound having at least three silicon-bonded hydrogen atoms per molecule. In this embodiment, starting material (E) can be a SiH-functional organosilicon compound, i.e., a compound having an average of one or more silicon-bonded hydrogen atoms per molecule. The crosslinker can include a silane and / or an organohydrogensilicon compound. Alternatively, the crosslinker can have an average of at least two silicon-bonded hydrogen atoms per molecule. The amount of crosslinker in the hydrosilylation-reactive hot melt adhesive composition depends on various factors, including the SiH content of the crosslinker and the unsaturated group content of the starting materials (A), (B), and (C), but the amount of crosslinker can be sufficient to provide a molar ratio of SiH groups in the hot melt adhesive composition to terminal aliphatic unsaturated organic groups in the hot melt adhesive composition (commonly referred to as the total SiH:Vi ratio) in the range of 0.3:1 to 5:1, alternatively 0.1:10 to 10:1. The crosslinker can have a monomeric or polymeric structure. If the crosslinker has a polymeric structure, the polymeric structure can be linear, branched, cyclic, or resinous. If the crosslinker is a polymer, it can be a homopolymer or a copolymer. The silicon-bonded hydrogen atoms in the crosslinker can be located at terminal, pendant, or both terminal and pendant positions. The crosslinker can be a single SiH-functional compound. Alternatively, the crosslinker can include a combination of two or more SiH-functional compounds. The crosslinker can be two or more organohydrogenpolysiloxanes that differ in at least one of the following characteristics: structure, average molecular weight, viscosity, siloxane units, and sequence.

[0107] The crosslinker has the formula R M4 uu SiH vv where the subscript uu is 0, 1, 2, or 3, and the subscript vv is 1, 2, 3, or 4, with the proviso that the quantity (uu+vv)=4. M4 are independently a halogen atom or a monovalent hydrocarbyl group, e.g., R MR is a monovalent hydrocarbyl group as described above for M4 Suitable halogen atoms for include chlorine, fluorine, bromine, and iodine, and alternatively chlorine. Suitable silanes for the crosslinker include trichlorosilane (HSiCl) and MeHSiCl.

[0108] Alternatively, the organohydrogensilicon compound for the crosslinker may be HR M5 2SiO 1 / 2 ,R M5 3SiO 1 / 2 , H.R. M5 SiO 2 / 2 , R M5 2SiO 2 / 2 , R M5 SiO 3 / 2 , HSiO 3 / 2 , and SiO 4 / 2 In the above formula, each R M5 is independently selected from the monovalent hydrocarbyl groups free of terminal aliphatic unsaturation described above.

[0109] The crosslinking agent is Formula (III):R M5 3SiO(R M5 2SiO) ww (R M5 HSiO) xx SiR M5 3. Formula (IV):R M5 2HSiO(R M5 2SiO) yy (R M5 HSiO) zz SiR M5 2H, or The polyorganohydrogensiloxane may include a combination thereof.

[0110] In the above formulas (III) and (IV), the subscript ww has an average value ranging from 0 to 2000, the subscript xx has an average value ranging from 2 to 2000, the subscript yy has an average value ranging from 0 to 2000, and the subscript zz has an average value ranging from 0 to 2000. As noted above, each R M5 are independently a monovalent organic group.

[0111] Polyorganohydrogensiloxanes for crosslinkers are exemplified by the following: a) dimethylhydrogensiloxy-terminated polydimethylsiloxane; b) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane); c) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane; d) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane); e) trimethylsiloxy-terminated polymethylhydrogensiloxane; f)(CH3)2SiO 1 / 2 Units and SiO 4 / 2 a resin consisting essentially of units; and g) Polydiorganosiloxanes, including combinations thereof.

[0112] Methods for preparing linear, branched, and cyclic organohydrogenpolysiloxanes suitable for use as crosslinkers, such as the hydrolysis and condensation of organohalosilanes, are well known in the art. Methods for preparing organohydrogenpolysiloxane resins suitable for use as crosslinkers are also well known, as exemplified in U.S. Patent Nos. 5,310,843, 4,370,358, and 4,707,531.

[0113] Alternatively, the organohydrogensilicon compound may comprise a cyclic organohydrogensilicon compound. Such organohydrogensilicon compounds are commercially available, including SYL-OFF™ SL2 CROSSLINKER and SYL-OFF™ SL12 CROSSLINKER, both of which are commercially available from Dow Silicones Corporation of Midland, Michigan, USA. The above organohydrogensilicon compounds and methods for their preparation are exemplified in WO2003 / 093349 and WO2003 / 093369.

[0114] In this embodiment, the exact amount of crosslinker in the hot melt adhesive composition will depend on various factors, including the type and amount of starting materials (A), (B), and (C), and the type and amount of any additional starting materials, if any. However, the amount of crosslinker in the hot melt adhesive composition may be from 0% to 25%, alternatively from 0.1% to 15%, alternatively from 1% to 5%, based on the total weight of all starting materials in the hot melt adhesive composition.

[0115] When the hot melt adhesive composition is condensation reactive, the crosslinker can be a silyl compound having at least two hydrolyzable substituents per molecule. In this embodiment, the crosslinker has the formula: R M6 (4-A) Six 4 A and oligomeric reaction products thereof, represented by the monomer of formula: M6 is a monovalent organic group, e.g., R 3 The monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups described above for X are, for example, alkyl groups having 1 to 6 carbon atoms. 4 is X 3 is a hydrolyzable substituent, as described above for X. Alternatively, X 4may be selected from an alkoxy group having 1 to 4 carbon atoms, a ketoxime group, an aminoxy group, an acetamido group, an N-methylacetamido group, or an acetoxy group, and the subscript A is 2 to 4, alternatively 3 to 4. A ketoxime group has the general formula -ONC(R M6 ) 2, wherein each R M6 independently represent an alkyl group of 1 to 6 carbon atoms or a phenyl group.

[0116] Specific examples of silanes suitable as crosslinkers in the condensation reactive hot melt adhesive composition include, but are not limited to, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, isobutyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane, (1,6-bis(trimethoxysilyl)hexane)glycidoxypropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, tetra(methylethylketoximo)silane, methyl-tris(methylethylketoximo)silane, and vinyl-tris(methylethylketoximo)silane, and combinations thereof.

[0117] In this embodiment, the crosslinker may be added to the condensation reactive hot melt adhesive composition in an amount of 0.01% to 10%, alternatively 0.3% to 5%, based on the combined weight of the starting materials (A), (B), and (C). The silane may be added for several purposes, including, but not limited to, providing stability to the composition as a moisture scavenger, aiding in network formation, and acting as an adhesion promoter.

[0118] (F) Inhibitor For example, if the composition is more reactive via hydrosilylation reactions, starting material (F) inhibitors may be added to the hot melt adhesive composition to modify the reaction rate of the starting material compared to a hot melt adhesive composition containing the same starting material but excluding the inhibitor. Inhibitors of the hydrosilylation reaction include (F1) acetylenic alcohols such as methylbutynol, ethynylcyclohexanol, dimethylhexynol and 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4- ethyl-1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol and 1-ethynyl-1-cyclohexanol, and combinations of two or more thereof; (F2) cycloalkenylsiloxanes, such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and combinations of two or more thereof; (F2) methylvinylcyclosiloxanes, exemplified by combinations of two or more thereof; (F3) ene-yne ​​compounds, such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and combinations of two or more thereof; (E4) triazoles, such as benzotriazole; (F5) phosphines; (F6) mercaptans; (F7) hydrazines; (F8) amines, such as tetramethylethylenediamine; (F9) fumarates, such as dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, and combinations of two or more thereof; (F10) maleates, such as diallyl maleate; (F11) nitriles; (F23) ethers; (F13) carbon monoxide; (F14) alcohols, such as benzyl alcohol; (F15) silylated acetylenic compounds; and combinations of two or more of (F1) to (F15).

[0119] The silylated acetylenic compound may be used to reduce or minimize the color (yellowing) of the reaction product produced in step 1) compared to a reaction product that does not include a silylated acetylenic compound or that includes an organic acetylenic alcohol, such as those described above. The silylated acetylene compounds are (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, bis(3-methyl-1- cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, (cyclohexyl-1-ethyn-1-oxy)trifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Alternatively, the inhibitor is exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or a combination thereof.Silylated acetylenic compounds useful as inhibitors can be prepared by methods known in the art, such as silylation of the acetylenic alcohols described above by reacting them with chlorosilanes in the presence of an acid acceptor.

[0120] The amount of inhibitor added to the melt adhesive composition will depend on various factors, including the desired pot life of the composition, the temperatures selected for processing and dispensing, the particular inhibitor used, and the selection and amounts of other starting materials used. However, if present, the amount of inhibitor may range from >0% to 1%, alternatively >0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, and alternatively 0.0025% to 0.025%, based on the total weight of all starting materials in the hot melt adhesive composition.

[0121] (G) Vehicle Vehicles (e.g., solvents and / or diluents) may optionally be added to the hot melt adhesive composition. The vehicle can facilitate the flow of the hot melt adhesive composition and the introduction of certain starting materials, such as polyorganosilicate resins, and / or the vehicle can act as a rheological aid in the hot melt adhesive composition. As used herein, a vehicle is a vehicle that aids in the flow of the starting materials used in the hot melt adhesive composition but does not essentially react with any of these starting materials. The vehicle can be selected based on the solubility and volatility of the starting materials in the hot melt adhesive composition. The solubility refers to whether the vehicle is sufficient to dissolve and / or disperse the starting materials of the hot melt adhesive composition. Volatility refers to the vapor pressure of the vehicle. If the vehicle is not volatile enough (the vapor pressure is too low), the vehicle may remain in the hot melt adhesive as a plasticizer, or the amount of time for the reactive hot melt adhesive to develop its physical properties may be longer than desired.

[0122] Suitable vehicles include polyorganosiloxanes having suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, available from Dow Silicones Corporation of Midland, Michigan, USA, in the range of 0.65 to 1.5 centistokes (cSt).

[0123] Alternatively, the vehicle may be an organic solvent, such as an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether; a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran; petrol; mineral spirits; naphtha; n-methylpyrrolidone; or a combination thereof.

[0124] The amount of vehicle can depend on various factors, including the type of vehicle selected and the amount and type of other starting materials selected for the hot melt adhesive composition. However, the amount of vehicle may range from 1% to 99%, alternatively from 2% to 50%, based on the total weight of all starting materials in the composition. Starting material (G) may be one vehicle. Alternatively, starting material (G) may include two or more different vehicles.

[0125] Moisture scavenger Component (H) is a moisture scavenger that may be optionally added to the hot melt adhesive composition. The moisture scavenger can be added to bind water from various sources that may reduce the shelf life of the hot melt adhesive composition. For example, if the hot melt adhesive composition is condensation reactive, the moisture scavenger can bind by-products of the condensation reaction, such as water and / or alcohol.

[0126] An example of an adsorbent suitable for the moisture scavenger may be inorganic particulates. The adsorbent may have a particle size of 10 micrometers or less, alternatively 5 micrometers or less. The adsorbent may have an average pore size sufficient to adsorb water and alcohol, for example, 10 Å (angstroms) or less, alternatively 5 Å or less, or even 3 Å or less. Examples of adsorbents include zeolites such as chabazite, mordenite, and analcime; molecular sieves such as alkali metal aluminosilicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof.

[0127] Examples of commercially available moisture scavengers include dry molecular sieves, such as 3 Å (angstrom) molecular sieves available from Grace Davidson under the SYLOSIV™ trademark and Zeochem of Louisville, Kentucky, USA under the PURMOL™ trademark, and 4 Å molecular sieves, such as Doucil zeolite 4A available from Ineos Silicas of Warrington, England. Other useful molecular sieves include MOLSIV ADSORBENT TYPE 13X, 3A, 4A, and 5A, all of which are available from UOP of Illinois, USA; SILIPORITE NK 30AP and 65xP from Arkema of King of Prussia, Pennsylvania, USA; and molecular sieves available from W.R. Grace of Maryland, USA.

[0128] Alternatively, the moisture scavenger may bind water and / or other by-products by chemical means. The amount of silane crosslinker added to the composition (in addition to any amount added as (E) crosslinker) may function as a chemical moisture scavenger. Without wishing to be bound by theory, it is believed that the chemical moisture scavenger may be added to the dry portion of a multi-part composition to keep the composition free of water after the portions of the composition are mixed together. For example, alkoxysilanes suitable as moisture scavengers have boiling points above 150°C that can withstand the process temperatures for producing hot melt adhesive compositions, and include phenyltrimethoxysilane, tetraethoxysilane, isobutyltrimethoxysilane, vinyltriethoxysilane, and combinations thereof.

[0129] The amount of moisture scavenger will depend on the particular moisture scavenger selected, however, if the moisture scavenger is a chemical moisture scavenger, the amount may range from 0% to 5%, alternatively 0.1% to 1%, based on the total weight of all starting materials in the composition.

[0130] (I) Filler Component (I) is a filler. The filler may include inorganic fillers such as fume silica, silica aerogel, silica xerogel, or precipitated silica, pyrogenic silica, diatomaceous earth silica, quartz powder, ground quartz, aluminum silicate, mixed aluminum and magnesium silicates, zirconium silicate, mica powder, calcium carbonate such as precipitated calcium carbonate or ground calcium carbonate, glass powder and fiber, pyrogenic oxide and rutile forms of titanium dioxide, barium zirconate, barium sulfate, barium metaborate, boron nitride, lithopone, oxides of iron, zinc, chromium, zirconium, and magnesium, various forms of alumina (hydrated or anhydrous), graphite, talc, diatomaceous earth, chalk sand, carbon black, and clays such as calcined clay, and organic materials such as phthalocyanines, cork powder, sawdust, synthetic fibers, and synthetic polymers (polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyvinyl chloride). Fillers are known in the art and commercially available. For example, fumed silica is known in the art and is sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, USA. Ground silica is sold under the name MIN-U-SIL by US Silica of Berkeley Springs, WV. Suitable precipitated calcium carbonates include Winnofil™ SPM from Solvay SA of Brussels, Belgium, and Ultra-pflex™ and Ultra-pflex™ 100 from Specialty Minerals Inc. of New York, USA. Fillers may be added in amounts up to 30%, alternatively 5% to 15%, based on the total weight of all starting materials in the hot melt adhesive composition.

[0131] The filler may optionally be treated with a filler treating agent. The amount of filler treating agent may vary depending on factors such as the type of treating agent selected, the type and amount of treated particulates, and whether the particulates are treated before being added to the composition or whether they are treated in situ. However, the filler treating agent may be used in an amount of 0.01% to 20%, alternatively 0.1% to 15%, alternatively 0.5% to 5%, based on the total weight of all starting materials in the hot melt adhesive composition. Particulates, such as fillers, physical moisture scavengers, and / or certain colorants, when present, may optionally be surface-treated with a filler treating agent. The particulates may be treated with a filler treating agent before being added to the hot melt adhesive composition or in situ. The filler treating agent may include alkoxysilanes, alkoxy-functional oligosiloxanes, cyclic polyorganosiloxanes, hydroxyl-functional oligosiloxanes, such as dimethylsiloxane or methylphenylsiloxane, or fatty acids. Examples of fatty acids include stearates, such as calcium stearate.

[0132] Some representative organosilicon filler treating agents that can be used include compositions commonly used to treat silica fillers, such as organochlorosilanes, organosiloxanes, organodisilazanes, e.g., hexaalkyldisilazanes, and organoalkoxysilanes, e.g., CH 13 Si(OCH3)3, C8H 17 Si(OC2H5)3, C 10 H 21 Si(OCH3)3, C 12 H 25 Si(OCH3)3, C 14 H 29 Si(OC2H5)3, and C6H5CH2CH2Si(OCH3)3. Other treating agents that may be used include alkyl thiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof.

[0133] Alternatively, the filler treating agent may have the formula: R M7 BSi(OR M8 ) (4-B) where the subscript B can have a value of 1 to 3, or alternatively, the subscript B=3. M7 R is independently a monovalent organic group, for example, a monovalent hydrocarbyl group of 1 to 50 carbon atoms, alternatively a monovalent hydrocarbyl group of 8 to 30 carbon atoms, alternatively a monovalent hydrocarbyl group of 8 to 18 carbon atoms. M7 R is exemplified by alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl (including branched and linear isomers of each) and aromatic groups such as benzyl and phenylethyl. M7 can be saturated or unsaturated, and branched or unbranched. Alternatively, R M7 can be saturated and unbranched.

[0134] Each R M8 are independently saturated hydrocarbon groups of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. Filler treating agents are exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof.

[0135] Alkoxy-functional oligosiloxanes may also be used as filler treating agents. For example, suitable alkoxy-functional oligosiloxanes include those of the formula (R M9 O) C Si(OSiR M10 2nd Round M11 ) (4-C) In this formula, the subscript C is 1, 2, or 3, or alternatively, the subscript C=3. M9 can be an alkyl group. M10 can be an unsaturated monovalent hydrocarbon group of 1 to 10 carbon atoms. M11may be an unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.

[0136] (J) Colorant Starting material (J) is a colorant (e.g., dye and / or pigment) that can be optionally added to the hot melt adhesive composition. Examples of suitable colorants include indigo, titanium dioxide, Stan-Tone 50SP01 Green or Stan-Tone 40SP03 Blue (commercially available from PolyOne), and carbon black. Representative, non-limiting examples of carbon black include Shawinigan acetylene black, commercially available from Chevron Phillips Chemical Company LP; SUPERJET™ carbon black (LB-1011) supplied by Elementis Pigments Inc., of Fairview Heights, IL USA; SR 511 supplied by Sid Richardson Carbon Co., of Akron, OH USA; colorant BA 33 iron oxide colorant (commercially available from Cathay Pigments (USA), Inc., Valparaiso, IN 46383 USA); and N330, N550, N762, N990 (from Degussa Engineered Carbons of Parsippany, NJ, USA). Examples of colorants are known in the art and are disclosed in U.S. Pat. Nos. 4,962,076; 5,051,455; and 5,053,442; and U.S. Patent Publication No. 2015 / 0376482 at paragraph

[0070] , which are incorporated herein by reference.

[0137] The amount of colorant will depend on various factors, including the type of colorant selected and the desired degree of coloration of the hot melt adhesive, as well as the selection of starting materials in the hot melt adhesive composition. For example, the hot melt adhesive composition may contain 0 to 10%, alternatively 0.001% to 5%, of colorant, based on the total weight of all starting materials in the hot melt adhesive composition.

[0138] (K) Fluorescent whitening agent The starting material (K) is, for example, an optical brightener that can be added to the hot melt adhesive composition to help ensure good dispensing when the hot melt adhesive composition is dispensed onto a substrate. Optical brighteners can be any chemical compound that absorbs light in the ultraviolet and violet regions of the electromagnetic spectrum (usually 340-370 nm) and re-emits light in the blue region (usually 420-470 nm) by fluorescence, and also has good heat resistance. Exemplary optical brighteners include stilbenes, such as 4,4'-diamino-2,2'-stilbenedisulfonic acid, coumarins, imidazolines, diazoles, triazoles, and benzoxazolines. Optical brighteners such as 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), available commercially as TINOPAL™ OB from BASF Corporation of Southfield, Michigan, USA, are commercially available. When present, the amount of optical brightener may be from 1 ppm to 1%, or alternatively from 0.01% to 0.05%, based on the total weight of all starting materials in the hot melt adhesive composition.

[0139] (L) Corrosion inhibitor Starting material (L) is a corrosion inhibitor that may be optionally added to the hot melt adhesive composition. Examples of suitable corrosion inhibitors include benzotriazole, mercaptabenzotriazole, mercaptobenzothiazole, and commercially available corrosion inhibitors, such as 2,5-dimercapto-1,3,4-thiadiazole derivative (CUVAN® 826) and alkyl thiadiazole (CUVAN® 484) from R.T. Vanderbilt of Norwalk, Connecticut, USA. If present, the amount of corrosion inhibitor can be 0.05% to 0.5% based on the total weight of all starting materials in the hot melt adhesive composition.

[0140] (M) Anti-aging additive The starting material (M) is an optional anti-aging additive that can be added to the hot melt adhesive composition. The anti-aging additive can include (M1) an antioxidant, (M2) a UV absorber, (M3) a UV stabilizer, (M4) a thermal stabilizer, or a combination of two or more of (M1), (M2), (M3), and (M4). Suitable antioxidants are known in the art and commercially available. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants and stabilizers. Phenolic antioxidants include fully hindered phenols and partially hindered phenols. Alternatively, the stabilizer can be a sterically hindered amine such as a tetramethylpiperidine derivative. Suitable phenolic antioxidants include vitamin E and IRGANOX™ 1010 from Ciba Specialty Chemicals, USA. IRGANOX™ 1010 contains pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate). Examples of UV absorbers include phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (TINUVIN™ 571). Examples of UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; methyl 1,2,2,6,6-pentamethyl-4-piperidyl / sebacate; and combinations thereof (TINUVIN™ 272). These and other TINUVIN™ additives, such as TINUVIN™ 765, are commercially available from Ciba Specialty Chemicals of Tarrytown, NY, USA. Other UV and light stabilizers are commercially available, examples being LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from EI du Pont de Nemours and Company of Delaware, USA. Oligomeric (high molecular weight) stabilizers may alternatively be used, for example, to minimize the possibility of the stabilizer migrating from the composition or its cured product.An example of an oligomeric antioxidant stabilizer (specifically, a hindered amine light stabilizer (HALS)) is Ciba TINUVIN™ 622, which is the dimethyl ester of butanedioic acid copolymerized with 4-hydroxy-2,2,6,6-tetramethyl-l-piperidineethanol. Thermal stabilizers can include metal salts of Ce, Cu, Zr, Mg, Fe, or Zn, such as iron oxide, carbon black, iron carboxylates, cerium hydrate, barium zirconate, cerium octoate, and zirconium octoate, and porphyrins. The amount of antiaging additive depends on various factors, including the specific antiaging additive selected and the desired antiaging benefit. However, the amount of antiaging additive may be 0 to 5%, alternatively 0.001% to 1%, alternatively 0.1% to 4%, or alternatively 0.5% to 3%, based on the total weight of all starting materials in the hot melt adhesive composition.

[0141] When selecting starting materials for the hot melt adhesive compositions described above, certain starting materials described herein may have multiple functions, and therefore there may be overlap between types of starting materials. For example, certain alkoxysilanes may be useful as filler treating agents and adhesion promoters in any hot melt adhesive composition; alternatively, such alkoxysilanes may also be useful as moisture scavengers and / or crosslinkers in condensation-reactive hot melt adhesive compositions. Carbon black may be useful as a colorant and / or filler.

[0142] In one embodiment, the hot melt adhesive composition can be prepared by adding (A) the above-described polyolefin-polydiorganosiloxane block copolymer to a moisture-curable hot melt adhesive composition, as described in U.S. Patent Publication No. 2015 / 0376482 to Bekemeier et al., where the polyolefin-polydiorganosiloxane block copolymer can be in an amount of at least 0.5%, alternatively 0.5% to 20%, based on the total weight of all starting materials in the hot melt adhesive composition.

[0143] Method for making a hot melt adhesive composition The hot melt adhesive composition may be prepared by a method comprising combining starting materials (A), (B), and (C), and optionally one or more additional starting materials (D), (E), (F), (G), (H), (I), (J), (K), (L), and (M). The combining may be carried out by any convenient means, such as feeding the starting materials into an extrusion apparatus and mixing the starting materials, optionally removing volatile materials, such as the vehicle, if present, to recover the hot melt adhesive composition. The hot melt adhesive composition may have a nonvolatile content of 97.5% to 100%, alternatively 98.5% to 100%, alternatively 99% to 100%.

[0144] The above-described vehicle can be used to prepare a hot melt adhesive composition. For example, one or more starting materials, such as a polyorganosilicate resin, can be dissolved or dispersed in the vehicle. The vehicle aids in the flow and introduction of the starting materials. However, some or all of the vehicle may be removed in a continuous process to produce the hot melt adhesive composition. In one embodiment, the hot melt adhesive prepared by solidifying the hot melt adhesive composition contains 0% to 2.5%, alternatively 0% to 0.5%, of the vehicle.

[0145] Typically, to prepare a hot melt adhesive composition, starting materials including (A), (B), and (C) and any additional starting materials are fed into a continuous mixing apparatus. The order of addition to the apparatus is not critical to the production of the hot melt adhesive composition. If the hot melt adhesive composition is condensation-reactive and the polyorganosilicate resin has more than 0.7% silanol, it may be desirable to add any silane crosslinkers and catalysts that may be used with the polyorganosilicate resin to effect the reaction and remove volatile reaction by-products (e.g., water or alcohol). The continuous mixing apparatus must be capable of mixing the starting materials and should include a means for removing volatile materials, such as the by-products and vehicle. Typically, an extrusion apparatus, such as a devolatilizing twin-screw extruder, is used. When using an extrusion apparatus, the starting materials are fed into the extruder and heated at temperatures between 50°C and 250°C, or alternatively, between 110°C and 190°C. Heating the starting materials also reduces their viscosity, making them easier to mix. In one embodiment, the starting materials (A) polyolefin-polydiorganosiloxane block copolymer, (B) polydiorganosiloxane, (C) polyorganosilicate resin, and (G) vehicle are first fed into an extrusion device. If the hot melt adhesive composition is reactive, the catalyst and crosslinker can be added simultaneously or at a later point in the process. When a hydrosilylation-reactive hot melt adhesive composition is being prepared, the inhibitor may be added before the catalyst.

[0146] Vacuum can be applied in single or multiple stages on a continuous mixing device (e.g., a devolatilizing extruder). Using multiple vacuum stages can be beneficial for removing the vehicle. Because certain starting materials, such as crosslinkers, can be volatile, any volatile starting materials can be added after some or all of the solvent has been removed to prevent removal of the volatile starting materials by the solvent. Those skilled in the art can prepare hot melt adhesive compositions from the starting materials described herein using processing techniques described, for example, in U.S. Pat. No. 8,580,073, column 7, line 28 to column 8, line 24, U.S. Patent Publication No. 2008 / 0300358, or U.S. Patent Publication No. 2015 / 0376482.

[0147] How to use / apply The hot melt adhesive compositions described herein can be used in an assembly process that includes 1) dispensing the molten hot melt adhesive composition onto a substrate; 2) assembling the substrate with the silicone hot melt adhesive composition and one or more additional substrates after step 1) and simultaneously with step 3); and 3) cooling the hot melt adhesive. Upon cooling, the hot melt adhesive composition solidifies to become an adhesive and / or sealant. The assembly process can optionally further include: 4) curing the hot melt adhesive composition during and / or after step 3). The hot melt adhesive compositions and processes described herein are useful for assembling electronic devices. Dispensing of the hot melt can be by controlled and timed compressed air, positive displacement, spraying, and any other convenient means known in the art.

[0148] The substrate (and any additional substrates) can be any component of an electronic device. The substrate can include a construction material selected from the group consisting of glass, plastic, silicone elastomer, metal, and combinations thereof. Exemplary plastics include glass-filled polycarbonate, fiberglass, polytetrafluoroethylene, and polyvinyl chloride. Exemplary metal substrates include aluminum, magnesium, and stainless steel. [Example]

[0149] These examples are intended to illustrate some embodiments of the invention and should not be construed as limiting the scope of the invention as set forth in the claims. References should not be considered prior art unless otherwise indicated.

[0150] Reference Example A - Procedure for the silylation of di-polyethylene-zinc with dimethylhydrogenchlorosilane (HMe2SiCl) Dipolyethylene zinc and Isopar (Mw=1580 Da, 10 mM) were placed in a vial. The vial was heated at 120°C until its contents became clear and homogeneous. Dimethylhydrogenchlorosilane and NMI were added to the vial. The vial was heated at 90°C for 3 hours. Iodine (I2) was then added to quench any unreacted dipolyethylene zinc. The resulting product was 1 The molar equivalents of HMe2SiCl and the conversion to products are shown below. [ka]

[0151] Reference Example A showed that when a relatively volatile chlorosilane was used, improved silylation could be achieved with an additional equivalent of chlorosilane.

[0152] Reference Example B - Procedure for the silylation of di-polyethylene-zinc with diphenylhydrogenchlorosilane (HPh2SiCl) Example A was repeated except that HPh2SiCl was used instead of HMe2SiCl, and the results are shown below. [ka]

[0153] Reference Example B demonstrated that complete silylation of di-polyethylene-zinc was possible using NMI as an additive.

[0154] Reference Example C - Procedure for the silylation of di-polyethylene-zinc with H2PhSiCl Dipolyethylene zinc and Isopar (Mw=1580 Da, 10 mM) were placed in a vial. The vial was heated at 120°C until the contents became clear and homogeneous. An additive selected from NMI or a blend of NMI and TMEDA, and phenyl, dihydrogen, and chlorosilane were added to the vial. The vial was heated for a certain period of time. Iodine (I2) was then added to quench the unreacted dipolyethylene zinc. The resulting product was 1 The molar equivalents of chlorosilane, molar equivalents of additive, heating time and temperature, and the conversion to product are shown below. [ka]

[0155] Reference Example C showed that complete silylation with phenyl, dihydrogen, chlorosilane was observed under the conditions described in Entry 6. At least one equivalent of NMI was able to complete the hydrosilylation. For comparison purposes, a blend of NMI and another amine base was used as the additive in Entry 5.

[0156] Reference example D Dipolyethylene zinc and Isopar (Mw=1080 Da, 10 mM) were placed in a vial. The vial was heated at 120°C until the contents became clear and homogeneous. Phenyl, dihydrogen, chlorosilane, and additives were added to the vial. The vial was heated at 100°C for 1 hour. I2 was then added to quench any unreacted dipolyethylene zinc. The resulting product was 1 The results of the conversion to additives and products are shown below. [ka]

[0157] Reference Example D showed that complete silylation was observed under the conditions tested using 4-dimethylaminopyridine and pyridine-N-oxide as additives. This example also showed that N-methylpyridone and DMPU can be used as additives to enhance silylation, as more silyl polymer is formed as shown in entries 2 and 3 than in the control without additives (entry 8).

[0158] Reference example E Example A was repeated using phenylhydrogendichlorosilane (HPhSiCl) instead of HMeSiCl and 1.2 equivalents of NMI instead of 2 equivalents as the additive, and the results are shown below. [ka]

[0159] Reference Example E showed that even when the amount of HPhSiCl2 was reduced, substitution occurred at only one of the two Si-Cl bonds.

[0160] Reference example F Dipolyethylene zinc and Isopar (Mw=1205 Da, 10 mM) were placed in a vial. The vial was heated at 120°C until the contents became clear and homogeneous. Dimethylhydrogeniodosilane (HMe2Sil) and NMI were added to the vial. The vial was heated at 110°C for 3 hours. I2 was then added to quench any unreacted dipolyethylene zinc. The resulting product was 1 The molar equivalents of HMe2Sil and the conversion to the product are shown below. [ka]

[0161] Reference Example F showed that NMI also promotes silylation with halosilanes other than chlorosilanes (e.g., iodosilane). In the absence of NMI, the iodosilane was not sufficiently electrophilic to react completely with dipolyethylene zinc under the conditions tested in this example.

[0162] Reference example G Silylation of ethylene / octenyl polymerylzinc with HPhSiCl was carried out as follows: In a glovebox, a 20 mL vial was charged with copolymerylzinc (Mn = 1940 Da, 30.66% octene, 3.10% polymer in Isopar™ E, 14.95 g, 0.117 mmol, 0.500 equiv.). The mixture was stirred and heated to 110 °C until the mixture became clear and homogeneous. NMI (22.5 μL, 0.282 mmol, 1.20 equiv.) was added, followed by chlorophenylsilane (37.6 μL, 0.282 mmol, 1.20 equiv.). The mixture was stirred for 1 hour. A portion of the solution was removed and quenched with excess iodine for conversion analysis. The polymer solution was poured into excess methanol, causing the polymer to precipitate. The polymer was isolated by filtration and dried in a vacuum oven. [ka]

[0163] Reference Example G demonstrated that silylation with ethylene / octene copolymeryl zinc was possible using NMI.

[0164] Reference Example: General Preparation Procedure for H-Silyl-Terminated Organometallics Polymerizations were conducted in a 2L PARR batch reactor. The reactor was heated with an electric heating mantle and cooled with an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system were controlled and monitored by a CAMILE TG process computer. The bottom of the reactor was fitted with a dump valve that discharged the reactor contents into a stainless steel dump pot. Both the pot and the tank were purged with nitrogen, and the dump pot was vented to a 30-gallon blow tank. All solvents used for polymerization or catalyst make-up were passed through a solvent purification column to remove any impurities that could affect the polymerization. 1-Octene, Isopar™ E, and toluene were passed through two columns: the first column containing A2 alumina, the second column containing Q5. Ethylene was passed through two columns: the first column containing A204 alumina and 4Å molecular sieves, and the second column containing the Q5 reactant. The nitrogen used for transfer was passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5.

[0165] Depending on the desired reactor load, the desired amount of Isopar™ E and / or toluene solvent and / or 1-octene was added to the load column via a shot tank. The load column was filled to the load set point using an electronic balance on which the load column was placed. After the addition of the liquid feed, the reactor was heated to the polymerization temperature set point. If ethylene was used, it was added to the reactor when the reactor was at reaction temperature to maintain the reaction pressure set point. The ethylene addition rate was monitored with a Micro-Motion flow meter.

[0166] The scavenger, MMAO-3A (commercially available from Akzo Nobel), was handled in an inert glove box, drawn into a syringe, and pressure-transferred to the catalyst shot tank. This was followed by three rinses with 5 mL of toluene each before injection into the reactor. The chain shuttling agent was handled in an inert glove box, drawn into a syringe, and pressure-transferred to the catalyst shot tank. This was followed by three rinses with 5 mL of toluene each before injection into the reactor. The procatalyst and activator were mixed with the appropriate amount of purified toluene to obtain a solution of the desired molar concentration. The catalyst and activator were handled in an inert glove box, drawn into a syringe, and pressure-transferred to the catalyst shot tank. This was followed by three rinses with 5 mL of toluene each. The run timer was started immediately after catalyst addition. Ethylene, if used, was then added via CAMILE to maintain the reaction pressure set point in the reactor. These polymerizations were conducted for either a 10-minute run or the targeted ethylene uptake. The agitator was then stopped, and the bottom dump valve was opened to drain the reactor contents into a clean dump pot that had been stored in a 130°C oven for >60 minutes prior to use to drive off excess moisture absorbed onto the metal surface. Once the reactor contents were drained into the dump pot, the normal flow of nitrogen inerting was switched to argon via a ball valve. Argon was allowed to flow for a calculated period, allowing for five gas exchanges within the pot. Once argon inerting was complete, the dump pot was removed from the fixture, and a secondary lid with inlet and outlet valves was sealed onto the top of the pot. The pot was then inerted with argon via the supply line and inlet / outlet valves for an additional five gas exchanges. Once complete, the valve was closed. The pot was then transferred to a glove box without exposing the contents to outside air.

[0167] Sample preparation according to the general procedures of Reference Examples I to H A homopolyethylene sample was prepared according to the general procedure of Reference Example H using the following conditions: 120 °C, 23 g initial ethylene addition, 600 g toluene, 10 μmol MMAO-3A, ​​and 1.2 equivalents of activator relative to the procatalyst. The amount of procatalyst used was adjusted to achieve the desired efficiency. The reactor pressure and temperature were maintained constant by feeding ethylene during the polymerization and cooling the reactor as needed. The polymerization was carried out using bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate as the activator, bis(N-isobutyl-6-mesitylpyridin-2-amine)dimethylhafnium as the procatalyst, and bis(8-(dimethylsilyl)octyl)zinc as the chain shuttling agent. 1 H-NMR Mn: 1586 per chain, GPC Mn: 1310 per chain.

[0168] Poly(ethylene / octene) copolymer samples were prepared according to the general procedure of Reference Example H using the following conditions: 120°C, 23 g initial ethylene addition, 397 g Isopar™ E, 115 g 1-octene, 10 μmol MMAO-3A, ​​and 1.2 equivalents of activator relative to the procatalyst. The amount of procatalyst used was adjusted to achieve the desired efficiency. The reactor pressure and temperature were maintained constant by feeding ethylene during the polymerization and cooling the reactor as needed. Polymerizations were carried out using bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate as the activator, [N-[2,6-bis(1-methylethyl)phenyl]-α-[2-(1-methylethyl)-phenyl]-6-(1-naphthalenyl-C2)-2-pyridinemethanaminato]dimethylhafnium as the procatalyst, and bis(8-(dimethylsilyl)hexyl)zinc as the chain shuttling agent. GPC Mn: 25,020 per chain, comonomer incorporation: 48% 1-octene.

[0169] Reference example J This Reference Example J demonstrates the water wash method used to purify mono-SiH-terminated polyethylene. 0.90 g of mono-SiH polyethylene prepared as described above was diluted to 10% in toluene in a 100 mL round-bottom flask containing a magnetic stir bar. The solution was heated by placing the flask in an aluminum block at 85°C. The mono-SiH-terminated polyethylene dissolved. Deionized water (6 g) was added and mixed for 5 minutes. Stirring was then stopped, and the aqueous layer (bottom) was removed using a plastic pipette. Excellent separation was achieved. Both phases were clear, and the pH of the wash water was alkaline.

[0170] The following process was carried out seven times at 85°C: Deionized water (4 g) was added and mixed for 5 minutes. The aqueous phase was removed. The resulting solution of toluene and mono-SiH terminated polyolefin was poured onto a Teflon™ sheet and allowed to dry overnight. The pH of the final water wash was slightly acidic, indicating successful removal of the imidazole.

[0171] Silyl-terminated polyolefins prepared as described in the above references can be used as starting materials for making polyolefin-polydiorganosiloxane block copolymers, such as polyethylene-polydimethylsiloxane copolymers.

[0172] Reference Example 1 - Polyethylene-polydimethylsiloxane diblock copolymer In this Reference Example 1, (AB) nA polyethylene-polydimethylsiloxane block copolymer with the structure was prepared as follows: 1.44 g (1 molar equivalent) of 63% telechelic MeHSi-terminated polyethylene (Mn: 1700 Da) was placed in a nitrogen-filled glove box in a 100 mL jar with a stir bar. 3.3361 g (1.234 equivalents; the stoichiometry was determined empirically beforehand to account for dead chain ends) of bis-silanol-terminated polydimethylsiloxane with a Mn of 4860 as determined by NMR (commercially available from Gelest, Inc. of Morrisville, Pennsylvania, USA: DMS-S21) was weighed directly into a vial inside the glove box. 7.3 mL of toluene was added, and the jar was heated to 103 °C to melt the polyethylene. The jar was gently agitated to avoid hitting the side walls. 350 μL of a 20 mg / mL solution of tris(pentafluorophenyl)borane in toluene was added, and bubbling was observed immediately. The jar was loosely capped, H2 gas was released, and the jar was heated at 100 °C overnight.

[0173] After running overnight, the reaction was cooled to room temperature and allowed to solidify. Isopropanol was added to the jar, and the resulting copolymer was broken up with a spatula. The mixture was stirred vigorously to break up debris. Stirring was stopped, and the copolymer was collected on a disposable plastic frit and then dried in a vacuum oven at 40°C. 4.50 g of material was collected. 1 H-NMR showed complete consumption of the Si-H functionality. High temperature GPC in trichlorobenzene showed approximately 6.5 repeat units of (polyethylene-polydimethylsiloxane).

[0174] In this Reference Example 2, a polyethylene-polydimethylsiloxane triblock copolymer having an ABA structure was prepared as follows: [ka]

[0175] In a glovebox: 150 mg of polyethylene-SiMeH (mono-terminated), 1.2 kDa, and 261 mg of telechelic hydroxyl-terminated PDMS (commercially available from Gelest as DMS-S21 oil, 1 molar equivalent of Si-OH) were heated to 120 °C. Subsequently, 6 μL of a 100 mg / mL solution of tris(pentafluorophenyl)borane (0.01 molar equivalent) in toluene was added, at which point hydrogen evolution was observed. The solution was stirred for 20 min, then removed from the glovebox, precipitated into isopropanol (iPrOH), and dried overnight under high vacuum at 60 °C to yield 415 mg of a white waxy solid. 1 The 1 H NMR spectrum was consistent with the formation of a triblock copolymer.

[0176] In this Reference Example 3, a polyethylene-polydimethylsiloxane triblock copolymer having an ABA structure was prepared as follows: [ka]

[0177] In a glovebox: 150 mg of polyethylene-SiMeH (mono-terminated), 1.2 kDa, and 1.62 g of telechelic hydroxyl-terminated PDMS (1 molar equivalent of Si-OH, DMS-S31) were heated to 120 °C. Subsequently, 6 μL of a 100 mg / mL solution of tris(pentafluorophenyl)borane (0.01 molar equivalent) in toluene was added. The solution was stirred for 20 min, then removed from the glovebox, precipitated into iPrOH, and dried overnight under high vacuum at 60 °C to yield 1.65 g of a white waxy solid. 1 The 1 H NMR spectrum was consistent with the formation of a triblock copolymer, with no apparent residual SiH functionality as indicated by the disappearance of the SiH resonance at 4.04 ppm.

[0178] Reference Example 4 - GPC Test Method Samples of copolymers and silyl-terminated polyolefins prepared as described in the Reference Examples above were analyzed by PolymerChar GPC-IR maintained at 160°C. Each sample was eluted through one PLgel 20µm 50x7.5mm guard column and four PLgel 20µm Mixed A LS 300x7.5mm columns with 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm butylated hydroxytoluene (BHT) at a flow rate of 1mL / min. A 16mg copolymer sample was weighed and diluted with 8mL of TCB by the instrument. For molecular weight, conventional calibration of polystyrene (PS) standards (Agilent PS-1 and PS-2) was used, with apparent units adjusted to homopolyethylene (PE) using the known Mark-Houwink coefficients for PS and PE in TCB at this temperature. Decane was used as an internal flow marker, and retention times were adjusted to this peak. For comonomer incorporation, a calibration curve for incorporation was generated using copolymers of known composition.

[0179] In this Example 5, to an oven-dried 1 L round-bottom flask and stir bar was added 55.28 g (18.96 mmol, 2.25 equiv.) of SiH-terminated poly(ethylene-co-octene) (M n 2672g / mol, effective M due to SiH 2916g / mol n , 13 The flask was placed in a glove box. A 150 mL jar was then filled with bis-silanol terminated PDMS (M by GPC) in toluene. n57.4 g (8.43 mmol, 1 equiv.) of a 50 wt.% solution of tris(pentafluorophenyl)borane (3130 g / mol) was weighed and dried over molecular sieves. The solution was poured into a round-bottom flask and rinsed with toluene several times until a total of approximately 350 mL of toluene was reached. A Stevens condenser was attached to the flask, and the flask was heated to 100 °C. A solution of tris(pentafluorophenyl)borane (52.5 mg, 0.09 mmol, 0.5 mol%) in 3 mL of toluene was prepared. After heating at 100 °C for 1.5 hours, the flask contained a slightly cloudy solution, but no polymer chunks remained. 0.5 mL of catalyst solution was then added, resulting in the formation of many bubbles. After 1 minute, the bubble formation slowed, and an additional 2 mL was added in three portions. A small amount of bubbling continued. After 1.5 hours, an aliquot was removed, dried under a stream of nitrogen on a hotplate set at 125°C, dissolved in tetrachloroethane, and analyzed by NMR, which showed the complete absence of SiH.

[0180] The material was removed from the glove box and poured into a tared steel pan. Any residual polymer on the inside of the flask was washed into the pan. The pan was covered with aluminum foil and placed in a fume hood to dry overnight.

[0181] The pan was then transferred to a vacuum oven set at 55°C over the weekend. 83.10 g of material was isolated as a white solid. Because some PDMS appeared to remain in conventional GPC, the material was redissolved in approximately 350 mL of toluene at 100°C and then cooled to room temperature. The slush was then added to a stirred solution of isopropanol (1 L) to precipitate. The mixture formed a milky white solution. To isolate the polymer, the mixture was poured into a 1 L container and centrifuged at 3000 rpm for 30 minutes. This process was completed in three batches. The supernatant was decanted through a disposable plastic frit. The compacted polymer was then poured onto the frit and allowed to dry. Residual polymer was rinsed from the centrifuge container with a small amount of isopropanol, and air was pumped through the filter cake for at least 1 hour, or until most of the liquid had been collected. The plastic frit was then covered and placed in a vacuum oven at 55°C overnight. High temperature liquid chromatography of the final material showed that the mixture contained 0.9 wt% free PDMS. The resulting composition represented 63.1% polyolefin in the triblock copolymer.

[0182] Industrial Applicability It has been found that polyolefin-polydiorganosiloxane block copolymers provide performance benefits to polyorganosiloxane hot melt adhesive compositions compared to comparable hot melt adhesive compositions containing polyolefin homopolymers instead of polyolefin-polydiorganosiloxane block copolymers. Without wishing to be bound by theory, it is believed that by grafting polyolefin onto the polydiorganosiloxane polymer block, the resulting copolymer can have excellent dispersibility in polydiorganosiloxane hot melt adhesive compositions containing polyorganosilicate resins and polydiorganosiloxane polymers, thereby improving the desired performance goal of increased stiffness / modulus. It is believed that crystallization of the dispersed polyolefin phase provides reinforcement similar to the way submicron dispersed particles or phases reinforce composites.

[0183] When a polyolefin-polydiorganosiloxane block copolymer is added to a polyorganosiloxane hot melt adhesive composition in an amount sufficient to provide a relatively small amount of polyolefin, such as polyethylene (e.g., including up to 5%), the viscosity or modulus can increase by more than an order of magnitude (compared to the same polyorganosiloxane hot melt adhesive composition without the copolymer) as a result of crystallization of the polyethylene phase upon cooling from the hot melt dispensing temperature. This is a significant improvement over conventional polyorganosiloxane hot melt adhesive compositions, which exhibit a much more gradual increase in viscosity or modulus with decreasing temperature.

[0184] Definitions and usage of terms Unless otherwise indicated by the context of the specification, all amounts, ratios, and percentages are by weight. The amounts of all starting materials in a composition add up to 100% by weight. The Brief Summary and Abstract of the Invention are incorporated herein by reference. Unless otherwise indicated by the context of the specification, the articles "a," "an," and "the" each refer to one or more. The disclosure of ranges includes the range itself and those subsumed therein, as well as the endpoints. For example, the disclosure of a range of 1 to 20 includes not only the range 1 to 20, including the endpoints, but also 1, 2, 3, 4, 6, 10, and 20 individually, and any other number subsumed within that range. Further, for example, the disclosure of a range of 1 to 20 includes 1 to 3, 2 to 6, 10 to 20, and 2 to 10, as well as any other subset subsumed within that range. Similarly, the disclosure of a Markush group includes the group as a whole and any individual members and subgroups subsumed therein. For example, disclosure of a Markush group hydrogen atom, alkyl group, alkenyl group, or aryl group individually includes the element alkyl; the sub-groups hydrogen, alkyl, and aryl; the sub-groups hydrogen and alkyl; and any other individual elements and sub-groups subsumed within that group.

[0185] "Periodic Table of the Elements" refers to the CRC Handbook of Chemistry and Physics, 68, published by CRC Press, Inc. in 1987. th "Periodic Table of the Elements" refers to the Periodic Table of the Elements as published in Edition 1989. Also, any reference to a Group(s) means the Group(s) reflected in this Periodic Table of the Elements, using the IUPAC system for numbering groups.

[0186] The term "creep" refers to the shear strain at break under a static load (constant stress). The creep resistance of the hot melt adhesives according to the present invention is a desirable property as it exhibits minimal or less creep than conventional polyorganosiloxane compositions that do not contain the polyolefin-polyorganosiloxane block copolymer.

[0187] The term "comprise," and its derivatives (e.g., comprising, comprises), is not intended to exclude the presence of any additional components, starting materials, steps or procedures, whether or not they are disclosed herein.

[0188] The term "green strength" refers to the solidification and increase in modulus when the reactive hot melt adhesive composition is cooled from the dispensing temperature to a lower temperature before the hot melt adhesive is fully cured. It is desirable that the hot melt adhesives prepared as described herein have high green strength after solidification after rapid and only small amounts of cooling, for example, after cooling by 5°C.

[0189] The term "hydrocarbyl" refers to groups containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic or acyclic groups. Monovalent hydrocarbyl groups include alkyl groups, including cycloalkyl groups, alkenyl groups, alkadienyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and alkynyl groups.

[0190] The term "colorant" includes any starting material used to impart color to hot melt adhesives prepared from the hot melt adhesive compositions described herein.

[0191] The term "telechelic" refers to a reactive polymer and means that the reactive polymer has reactive functional groups at the chain ends, which may have the same or different reactive functional groups. As used herein, either or both of A) the silyl-terminated polyolefin and (B) the polydiorganosiloxane may be telechelic, or neither may be telechelic.

[0192] The following abbreviations are used throughout the specification: [Table 1-1] [Table 1-2]

[0193] Embodiments of the invention In a first embodiment, the hot melt adhesive composition may be non-reactive, and the hot melt adhesive composition is formed by cooling the hot melt adhesive composition from the melt dispensing temperature to a lower temperature. In this embodiment, the starting materials include (A), (B), and (C) above, the substituents (R groups) on the starting materials do not react with each other, and (D) catalysts, (E) crosslinkers, and (F) inhibitors are typically not added to the non-reactive hot melt adhesive composition.

[0194] In a second embodiment, the hot melt adhesive composition is reactive and includes starting materials (A), (B), (C), and (D). Reactive hot melt adhesive compositions harden by both cooling and curing. When the hot melt adhesive composition is reactive, it may further include starting material (E) a crosslinker. When the hot melt adhesive composition is hydrosilylation-curable, starting material (D) includes the hydrosilylation catalyst described above. In a hydrosilylation-curable hot melt adhesive composition, one or more of starting materials (A), (B), and (C) have terminal aliphatically unsaturated hydrocarbyl groups capable of hydrosilylation reaction. In this embodiment, the (E) crosslinker may have silicon-bonded hydrogen atoms. In this embodiment, an inhibitor (F) may be added to control the cure rate of the hydrosilylation-curable hot melt adhesive composition.

[0195] When the hot melt adhesive composition is a condensation reaction curable hot melt adhesive composition, starting material (D) comprises a condensation reaction catalyst. In this embodiment, one or more of starting materials (A), (B), and (C) have silicon-bonded hydrolyzable substituents. In this embodiment, the condensation reaction curable hot melt adhesive composition may further comprise (H) a moisture scavenger.

[0196] Alternatively, the hot melt adhesive composition may be a dual cure composition, for example, containing both a hydrosilylation reaction catalyst and a condensation reaction catalyst.

[0197] In a third embodiment of the present invention, the hot melt adhesive composition comprises: (A) A polyolefin-polydiorganosiloxane block copolymer, the polyolefin-polydiorganosiloxane block copolymer having a unit formula (I): [ka] wherein each R 1 are independently selected monovalent hydrocarbyl groups, and each R3 are independently selected from hydrogen atoms and monovalent organic groups that are free of hydrolyzable functionality, and each R 5 are independently selected hydrogen-terminated polyolefins, and each R 6 are independently selected divalent polyolefins, and each R 10 are independently 3 and alkoxysilyl-functional hydrocarbylene-containing groups, wherein each subscript a is independently 1 or 2, each subscript b is independently 0 or a positive number, subscript w is 0 to 2, subscript x is 0 or a positive number, subscript y is 0 or a positive number, subscript z is 0 to 2, the quantity (w+y)≧1, and the quantity (x+z)≧1, with the proviso that when subscript w is 0, subscript z>0, and when subscript z=0, subscript w>0; (B) a polydiorganosiloxane; and (C) a polyorganosilicate resin.

[0198] In a fourth embodiment, the copolymer of the third embodiment has formula (IV): [ka] Formula (V): [ka] where the subscript c is ≥ 0. Formula (VI): [ka] Formula (VII): [ka] where the subscript d is ≥ 0. Formula (VIII): [ka] or a combination of two or more of formulas (IV), (V), (VI), and (VIII), In the formula, each R 1 are independently selected monovalent hydrocarbyl groups, and each R 3 are independently selected from hydrogen atoms and monovalent organic groups that are free of hydrolyzable functionality, and each R 5 are independently selected hydrogen-terminated polyolefin blocks, and each R 6 are independently selected divalent polyolefin blocks, and each R 10 are independently 3 and alkoxysilyl-functional hydrocarbylene-containing groups, wherein each subscript a is independently 1 or 2, and each subscript b≧0.

[0199] In a fifth embodiment, the copolymer of the fourth embodiment comprises: [ka] [ka] R represents an alkoxysilyl-functional hydrocarbylene-containing group having a formula selected from 10 wherein each R L is an oxygen atom, each R D is independently a divalent hydrocarbyl group of 2 to 18 carbon atoms, each subscript aa is independently 0, 1, or 2, alternatively 0 or 1, subscript D is 0 to 20, alternatively 1 to 10, E is 0 or greater, subscript F is 1 or greater, and subscript G is 1 or greater, and 4≦(E+F+G)≦50.

[0200] In a sixth embodiment, one or more of conditions (i) and (ii) in any one of the third, fourth, or fifth embodiments is met; Condition (i) is that each R 5 is the unit formula H[(CH2CH2) t (CHR 7 CH2) u ] gwhich is to have Condition (ii) is such that each R 6 has the unit formula [(CH2CH2) t (CHR 7 CH2) u g wherein the subscripts t and u have relative values such that 0 < t ≤ 1 and 0 ≤ u ≤ 1, and the subscript g ≥ 1, and each R 7 is an independently selected monovalent hydrocarbyl group having 2 to 20 carbon atoms.

[0201] In the seventh embodiment, the polyolefin-polydiorganosiloxane block copolymer in any one of the third, fourth, fifth, or sixth embodiments can react with (B) a reactive polydiorganosiloxane, (C) a polyorganosilicate resin, or both (B) and (C).

[0202] In the eighth embodiment, the hot melt adhesive composition in the seventh embodiment further includes an additional starting material selected from the group consisting of (D) a catalyst, (E) a crosslinking agent, (F) an inhibitor, (G) a vehicle, (H) a moisture scavenger, (I) a filler, (J) a colorant, (K) a fluorescent whitening agent, (L) a corrosion inhibitor, (M) a heat stabilizer, and combinations of two or more of (E), (F), (G), (H), (I), (J), (K), (L), and (M).

[0203] In the ninth embodiment, the polydiorganosiloxane in the composition of any one of the third to seventh embodiments has terminal hydroxyl groups (i.e., silanol terminals).

[0204] In the tenth embodiment, the polydiorganosiloxane in the ninth embodiment is polydimethylsiloxane.

[0205] In the eleventh embodiment, the polyorganosilicate resin in the ninth or tenth embodiment has a methyl group.

[0206] ​In a twelfth embodiment, in the composition of any one of the first to eleventh embodiments, the starting material (B) polydiorganosiloxane and the starting material (C) polyorganosilicate resin are: [ka] [ka] wherein each R L is an oxygen atom, and each R D are independently divalent hydrocarbyl groups of 2 to 18 carbon atoms; each subscript aa is independently 0, 1, or 2, alternatively 0 or 1; subscript D is 0 to 20, alternatively 1 to 10; E is 0 or greater; subscript F is 1 or greater; and subscript G is 1 or greater, and 4≦(E+F+G)≦50.

Claims

1. 1. A hot melt adhesive composition comprising: (A) A polyolefin-polyorganosiloxane block copolymer, the polyolefin-polyorganosiloxane block copolymer having a unit formula (I): 【Chemistry 1】 wherein each R １ are independently selected monovalent hydrocarbyl groups, and each R ３ is independently selected from monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups, and each R ５ is a monovalent polyolefin chain radical derived by removing one hydrogen atom from the end of a polyolefin chain, and each R ６ are independently selected divalent polyolefin chain groups derived from polyolefin chains, and each R １０ are independently R ３ and alkoxysilyl-functional hydrocarbylene-containing groups, wherein each subscript a is independently 1 or 2, each subscript b is independently 0 or a positive number, subscript w is 0 to 2, subscript x is 0 or a positive number, subscript y is a positive number, subscript z is 0 to 2, the quantity (w+y)≧1, and the quantity (x+z)≧1, with the proviso that when subscript w is 0, subscript z>0, and when subscript z=0, subscript w>0; (B) R Ｍ３ ３ SiO(R Ｍ３ ２ SiO) ｓｓ SiR Ｍ３ ３ wherein the subscript ss is the average value per molecule of said linear polydiorganosiloxane ranging from 2 to 2000, and each R Ｍ３ is an alkyl group or an aryl group; (C) Formula R Ｍ ３ SiO １／２ (In the formula, each R Ｍ independently represent a monovalent organic group) and a monofunctional (M) unit of the formula SiO ４／２ and an MQ resin consisting solely of tetrafunctional silicate (Q) units.

2. 1. A hot melt adhesive composition comprising: (A) A polyolefin-polyorganosiloxane block copolymer, the polyolefin-polyorganosiloxane block copolymer having a unit formula (I): 【Chemistry 2】 wherein each R １ are independently selected monovalent hydrocarbyl groups, and each R ３ is independently selected from monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups, and each R ５ is a monovalent polyolefin chain radical derived by removing one hydrogen atom from the end of a polyolefin chain, and each R ６ are independently selected divalent polyolefin chain groups derived from polyolefin chains, and each R １０ are independently R ３ and alkoxysilyl-functional hydrocarbylene-containing groups, wherein each subscript a is independently 1 or 2, each subscript b is independently 0 or a positive number, subscript w is 0 to 2, subscript x is 0 or a positive number, subscript y is 0 or a positive number, subscript z is 0 to 2, the quantity (w+y)≧1, and the quantity (x+z)≧1, with the proviso that when subscript w is 0, subscript z>0, and when subscript z=0, subscript w>0; (B) i) dimethylvinylsiloxy-terminated polydimethylsiloxane; ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane; iv) trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); v) trimethylsiloxy-terminated polymethylvinylsiloxane; vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane); viii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane); ix) phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxanes; x) dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane; xiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xiv) Trimethylsiloxy-terminated polymethylhexenylsiloxane xv) dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / methylhexenylsiloxane); xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xvii) A combination of two or more of the above i) to xvi). a reactive linear polydiorganosiloxane selected from (C) Formula R Ｍ ３ SiO １／２ (In the formula, each R Ｍ are independently selected monovalent organic groups), and monofunctional (M) units of the formula SiO ４／２ and an MQ resin consisting solely of tetrafunctional silicate (Q) units of the formula: (D) a hydrosilylation catalyst; (E) a hydrosilylation-curing crosslinker comprising a silyl compound having at least three silicon-bonded hydrogen atoms per molecule; (F) an inhibitor; (G) a vehicle selected from hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, or an organic solvent; (H) a moisture scavenger; (I) a filler; (J) a colorant; (K) an optical brightener; (L) a corrosion inhibitor; (M) a heat stabilizer; and additional starting materials selected from the group consisting of combinations of two or more of (E), (F), (G), (H), (I), (J), (K), (L), and (M). Hot melt adhesive compositions.

3. 1. A hot melt adhesive composition comprising: (A) A polyolefin-polyorganosiloxane block copolymer, the polyolefin-polyorganosiloxane block copolymer having a unit formula (I): 【Transformation 3】 wherein each R １ are independently selected monovalent hydrocarbyl groups, and each R ３ is independently selected from monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups, and each R ５ is a monovalent polyolefin chain radical derived by removing one hydrogen atom from the end of a polyolefin chain, and each R ６ are independently selected divalent polyolefin chain groups derived from polyolefin chains, and each R １０ are independently R ３ and alkoxysilyl-functional hydrocarbylene-containing groups, wherein each subscript a is independently 1 or 2, each subscript b is independently 0 or a positive number, subscript w is 0 to 2, subscript x is 0 or a positive number, subscript y is 0 or a positive number, subscript z is 0 to 2, the quantity (w+y)≧1, and the quantity (x+z)≧1, with the proviso that when subscript w is 0, subscript z>0, and when subscript z=0, subscript w>0; (B) The following formula (B2): X ３ R Ｍ ２ SiO-(R Ｍ ２ SiO) ｐｐ -SiR Ｍ ２ X ３ (In the formula, each ３ are independently selected hydrolyzable substituents, and each R Ｍ are independently selected monovalent hydrocarbyl groups free of aliphatic unsaturation, and the subscript pp is a value ranging from 100 to 10,000. a reactive linear polydiorganosiloxane having the formula: (C) Formula R Ｍ ３ SiO １／２ (In the formula, each R Ｍ represent an independently selected monovalent organic group), and a monofunctional (M) unit of the formula SiO ４／２ and an MQ resin consisting of tetrafunctional silicate (Q) units of the formula: (D) a condensation cure catalyst, (E) a condensation cure crosslinker, (F) an inhibitor, (G) a vehicle selected from hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, or an organic solvent, (H) a moisture scavenger, (I) a filler, (J) a colorant, (K) an optical brightener, (L) a corrosion inhibitor, (M) a heat stabilizer, and additional starting materials selected from the group consisting of combinations of two or more of (E), (F), (G), (H), (I), (J), (K), (L), and (M); Hot melt adhesive compositions.

4. Each R in (B) Ｍ３ 2. The hot melt adhesive composition of claim 1, wherein is a methyl group.

5. In the unit formula (I), subscript w=1, subscript x=0, subscript y=0, and subscript z=1, and said copolymer of (A) is of formula (IV): 【Chemistry 4】 4. The hot melt adhesive composition of claim 2 or 3, wherein

6. In unit formula (I), subscript w=2, subscript z=0, subscript x≧1, and subscript y≧0, and the copolymer has formula (V): 【Transformation 5】 4. The composition of claim 2 or 3, having the formula:

7. In the unit formula (I), subscript z=2, subscript w=0, subscript x≧0, and subscript y≧1, and the copolymer has the formula (VII): 【Transformation 6】 4. The composition of claim 1, wherein the subscript d is greater than or equal to 0.

8. (i) Each R ５ is the unit formula H [(CH ２ CH ２ ) ｔ (CHR ７ CH ２ ) ｕ ] ｇ and (ii) Each R ６ is the unit formula [(CH ２ CH ２ ) ｔ (CHR ７ CH ２ ) ｕ ] ｇ or (iii) both (i) and (ii), where the subscripts t and u are relative values, 0<t≦1, 0≦u≦1 (where t+u=1), and the subscript g≧2; ７ The composition of any one of claims 1 to 5, wherein: are independently selected monovalent hydrocarbyl groups of 2 to 20 carbon atoms.

9. (a) the polyolefin-polyorganosiloxane block copolymer has Si—H groups, and (B) the reactive linear polydiorganosiloxane having vinyl or hexenyl groups, and (C) the MQ resin is R Ｍ capable of reacting with the MQ resin if it has an alkenyl group capable of hydrosilylation with the Si—H group of the polyolefin-polydiorganosiloxane block copolymer, or (b) the polyolefin-polyorganosiloxane block copolymer is R of the unit formula (I): １０ (C) having an alkoxysilyl-functional hydrocarbylene group as the alkoxysilyl functional group, and capable of reacting with the MQ resin; or The composition according to claim 2, which is a combination of (a) and (b).

10. (a) the polyolefin-polyorganosiloxane block copolymer is a polyolefin-polyorganosiloxane block copolymer having a unit formula (I): １０ (B) X of formula (B2) ３ or (b) the polyolefin-polyorganosiloxane block copolymer is R of the unit formula (I): １０ (B) X of formula (B2) ３ a reactive linear polydiorganosiloxane having hydrolyzable substituents as (C) the composition of claim 3, capable of reacting with the MQ resin.

11. 11. The composition of any one of claims 1 to 10, wherein starting material (A) is present in an amount of at least 0.1 wt.%, based on the total weight of all starting materials in the composition.

12. Use of the hot melt adhesive composition according to any one of claims 1 to 11 in the assembly process of electronic devices.

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